Download or read book Catalytic Oxidative Dehydrogenation of Light Alkanes written by Ali Saberi Moghaddam and published by . This book was released on 1995 with total page 610 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Mechanistic Insights on the Oxidative Dehydrogenation of Light Alkanes Catalyzed by Boron based Catalysts written by Juan Mauricio Venegas and published by . This book was released on 2019 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Light olefins such as ethylene and propylene form the foundation of the modern chemical industry, with yearly production volumes well into the hundreds of millions of metric tons. Currently, these light olefins are mainly produced via energy-intensive steam cracking. Alternatively, oxidative dehydrogenation (ODH) of light alkanes to produce olefins allows for lower operation temperatures and extended catalyst lifetimes, providing valuable process efficiencies. This route has led to significant research interest due to the wide availability of natural gas from shale deposits. Advances in this area have still not yielded catalysts that are sufficiently selective to olefins for industrial implementation, and ODH still remains a holy grail of selective alkane oxidation research. Research into selective heterogeneous catalysts for the ODH of propane has led to the extensive use of vanadium oxide-based catalysts, and studies on the surface mechanism involved have been used to improve the catalytic activity of the material. Despite decades of research, however, selectivity towards propylene has not proven satisfactory at industrially-relevant conversions. In this thesis, I will present the serendipitous discovery and subsequent development of hexagonal boron nitride (hBN) and other boron-containing catalysts as selective ODH catalysts. Specifically, I will illustrate the evolution of our understanding of the chemical origin of the reactivity of these materials, which until our initial discovery were deemed chemically inert. By combining reactivity studies with spectroscopic characterization highlighted a unique interaction between boron and oxiygen that differs from that of metal oxides. This methodical characterization of catalytic activity and structural changes of hBN during ODH prompted us to zero in on oxidized boron species, not hBN itself, as the true catalyst of alkane oxidation. In turn, this discovery led us to describe a whole class of B-containing materials that share (and often improve upon) the catalytic performance of hBN. At this point, we decided to step away from material studies and instead improve our understanding on how the catalytic performance of hBN is affected by reactor operating parameters. In particular, we investigated the role of heat and mass transfer on catalytic performance. Unexpectedly, we were once again surprised by hBN when various experimental results during these efforts suggested the significance of gas phase chemistry on ODH performance. For example, we observed that upon dilution of hBN with an inert thermal conductor (to mitigate hotspot formation), the observed reactivity scales with total bed volume rather than hBN mass. Up until these studies, we expected all reactivity to stem from oxidized boron species, but these may be only a part of a more complex surface-gas phase reaction network. The final portion of this thesis presents our latest efforts to understand the role of each reactant on surface and gas phase reaction pathways. Within this work, we incorporate water into our reaction feeds to assess its influence as a source of gas phase radical species to carry out propane activation. Indeed, we observe significant rate enhancements by addition of water. This reactivity enhancement likely involves influencing reactive species concentrations primarily in the gas phase and, to a lesser extent, altering the surface composition during ODH. Overall, this thesis expands our understanding of B-based materials as ODH catalysts and highlights the importance of considering gas phase radical chemistry in future process development.

Download or read book Oxidative Dehydrogenation of Light Alkanes on Metal Oxide Catalysts written by Morris Dee Argyle and published by . This book was released on 2003 with total page 338 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Catalytic Activation and Functionalisation of Light Alkanes written by E.G. Derouane and published by Springer Science & Business Media. This book was released on 1998-02-28 with total page 508 pages. Available in PDF, EPUB and Kindle. Book excerpt: Light alkanes tend to be resistant to many forms of activation. The horizontal approach of the present book covers homogeneous, heterogeneous and biological catalysis, thus allowing readers to gain an awareness of progress and ideas in research areas different from their own. The book contains both general chapters, giving an overview of the subject, and specialised contributions that deal with the details and state of the art. A specialist report is also included which gives a critical insight into current progress and discusses future prospects and major challenges. Audience: Newcomers and senior researchers in the field of alkane activation. The mixed theoretical and practical approach will be of interest to researchers and industrialists alike.

Download or read book Synthesis and Investigation of Boron and Vanadium Based Catalysts for the Oxidative Dehydrogenation of Light Alkanes to Olefins written by Natalie Raquel Altvater and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Light olefins like ethylene and propylene are important building blocks for the chemical industry. Production of these chemicals exceeds 100 million metric tons each year, and they are used in all areas of society including automotive, medical, textile, and food packaging. These light olefins are traditionally produced via steam cracking which is an energy intensive process. The increasing availability of natural gas in the present chemical industry has shifted the feedstock for refinery processes and impacted the production volume of certain olefins, particularly propylene. As a result, there is a growing need for on-purpose propylene production methods to meet the market demands. Oxidative dehydrogenation (ODH) of propane to propylene is one potential pathway for increasing propylene production. Propane ODH offers lower temperature operation and does not suffer from catalyst deactivation from coke. This process still suffers from over oxidation of products and does not achieve propylene yields required for industrial implementation. Propane ODH has been studied extensively for vanadium oxide catalysts and more recently for boron-based catalysts. Despite the wealth of literature on these ODH catalyst there are still several open questions on the catalyst structure and reaction mechanisms that continue to motivate research to improve the catalytic systems. The understanding on the mechanism and structural features of boron-based has been significantly developed in recent years. This work serves to build on this knowledge and improve current knowledge on structure activity relationships for this system. Vanadium oxide catalysts have been the center of propane ODH for much longer than boron, and while literature agrees generally on the surface mechanism description of this system, there are open questions on different pathways in the mechanism and their influence on performance. The goal of this work is to show how synthesis spectroscopy, reaction engineering, and computation work combine to further the understanding of boron and vanadium oxide catalyst for propane ODH.

Download or read book Oxidative Dehydrogenation of Light Alkanes with Carbon Dioxide written by Marktus Alagtogra Atanga and published by . This book was released on 2016 with total page 140 pages. Available in PDF, EPUB and Kindle. Book excerpt: "Most experts studying the global ecosystem and climate suggest that rising anthropogenic CO2 emissions have contributed to significant global climate change in the last half-century. The development of effective strategies that convert CO2 into energy, fuels, and chemicals are greatly preferable to oceanic or geologic sequestration options because they offer the potential to create new commercially-viable products from renewable carbon feedstock. On the other hand, the selective oxidative dehydrogenation of light alkanes (C2-C4) to corresponding olefins, methane reforming, and methane coupling are the major challenges for producing valuable and versatile feedstocks. The oxidative dehydrogenation of light alkanes with carbon dioxide (ODAC) reaction is a sustainable approach to the production of value-added monomers with less environmental footprint than non-oxidative dehydrogenation reactions. This work involved the development of efficient catalysts for oxidative dehydrogenation reaction, methane coupling and reforming. Hydrothermal synthesis method was used to achieve isomorphous substitution of active single metal and bimetal promoters into the SAPO-34 zeolite support. Uniformly dispersed and highly active metal promoters anchored in the framework of the support were obtained. This is the first time of reporting success in isomorphous substitution of niobium, and vanadium metal promoters into the framework of CHA structure of SAPO-34 zeolite. The effect of different metal (indium, gallium, vanadium, niobium, and chromium) promoters and influence of CO2 as a soft oxidant in C-H bond scission were investigated. Catalyst characterizations were carried out using XRD, FTIR, and TPD, sorption, TGA and SEM techniques"--Abstract, page iii.

Download or read book Catalysts for the Oxidative Dehydrogenation of Alkanes at Millisecond Contact Times written by Derrick W. Flick and published by . This book was released on 2000 with total page 514 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Alkane Functionalization written by Armando J. L. Pombeiro and published by John Wiley & Sons. This book was released on 2019-03-11 with total page 680 pages. Available in PDF, EPUB and Kindle. Book excerpt: Presents state-of-the-art information concerning the syntheses of valuable functionalized organic compounds from alkanes, with a focus on simple, mild, and green catalytic processes Alkane Functionalization offers a comprehensive review of the state-of-the-art of catalytic functionalization of alkanes under mild and green conditions. Written by a team of leading experts on the topic, the book examines the latest research developments in the synthesis of valuable functionalized organic compounds from alkanes. The authors describe the various modes of interaction of alkanes with metal centres and examine theoxidative alkane functionalization upon C-O bond formation. They address the many types of mechanisms, discuss typical catalytic systems and highlight the strategies inspired by biological catalytic systems. The book also describes alkane functionalization upon C-heteroatom bond formation as well as oxidative and non-oxidative approaches. In addition, the book explores non-transition metal catalysts and metal-free catalytic systems and presents selected types of functionalization of sp3 C-H bonds pertaining to substrates other than alkanes. This important resource: Presents a guide to the most recent advances concerning the syntheses of valuable functionalized organic compounds from alkanes Contains information from leading experts on the topic Offers information on the catalytic functionalization of alkanes that allows for improved simplicity and sustainability compared to current multi-stage industrial processes Explores the challenges inherent with the application of alkanes as starting materials for syntheses of added value functionalized organic compounds Written for academic researchers and industrial scientists working in the fields of coordination chemistry, organometallic chemistry, catalysis, organic synthesis and green chemistry, Alkane Functionalization is an important resource for accessing the most up-to-date information available in the field of catalytic functionalization of alkanes.

Download or read book Development and Characterization of Oxyfunctionalized Boron Nitride Catalysts for the Oxidative Dehydrogenation of Light Alkanes to Olefins written by Theodore Agbi and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Light olefins like ethylene and propylene are platform chemicals integral to the chemical industry. Production of polymers, oxygenates, and other important chemical intermediates demand global production volumes that top 100 million metric tons per year. Production of these light olefins, traditionally through steam cracking, is one of the most energy intensive processes in petrochemical sector. Changing refinery feedstocks (i.e. increased availability of natural gas) have created both necessity and opportunity for 'On-Purpose' propylene technologies to meet propylene demands. The oxidative dehydrogenation of propane to propylene (ODHP) is an attractive alternative process to produce propylene. ODHP enables lower process temperatures and avoids coke deactivation of the catalyst, and has the potential to significantly ease energy, capital, and material intensities of industrial propylene production. To-date, metal oxide ODHP catalysts like vanadia-based catalysts-the previous state of the art ODHP catalyst-do not achieve competitive propylene yields to make them industrially viable. The pioneering work of our research group has identified BN-a material renowned for its chemical inertness-as a highly reactive, selective, and stable ODHP catalyst. Since this discovery, we have worked to understand the fundamental reaction mechanisms present and identify structure-performance relationships that may further develop this class of catalyst. To-date, we have developed extensive spectroscopic characterization capabilities to identify the oxyfunctionalized boron layer formed in situ which contains highly dynamic active species responsible for the high reactivity and selectivity observed. Understanding the activation of molecular O2 and functionality of the oxyfunctionalized layer has been a highly collaborative process requiring a myriad of complimentary spectroscopic and reaction studies to develop fundamental insights. As such, I will provide a comprehensive context of our evolving knowledge in this collaborative project that have since been published where possible and will focus mainly on the recent insights made in this work. The work presented in this dissertation characterizes and probes the reactivity of the highly dynamic oxyfunctionalized surface layer that has been correlated with the reactivity and selectivity observed on this catalyst. Herein, the coordination environment of B and extent of oxyfunctionalization were analyzed via X-ray Photoelectron Spectroscopy (XPS), X-ray Absorption Spectroscopy (XAS), and Attenuated Total Reflectance IR (ATR-IR) as a function of the reaction progress. Corresponding reaction studies show direct correlation between the development of tri-coordinated oxygenated B networks and the increasing reactivity and selectivity of the reaction during the catalyst's activation period. The significance of a set of reaction parameters was then examined to identify process levers conducive to oxyfunctionalization quantified by XPS. The acid-base activity of these surface tri-coordnated B networks in the oxyfunctionalized layer are examined via two prototypical reactions: (1) isopropanol decomposition and (2) formic acid decomposition. Catalytic reaction via flow through reactor and temperature programmed decomposition (TPD) studies using Diffuse Reflectance Infrared Fourier Transform IR spectroscopy (DRIFTs) and Mass Spectrometry (MS) are used to extract insights for the adsorption modes of alkoxides and formates their decomposition pathways. Observed surface reactions of isopropoxy intermediates under these conditions are used to understand possible surface reaction pathways available under ODHP conditions. The role of O2 in specific homogeneous pathways of the mixed hetero-homogeneous mechanism previously proposed by us and for supported boron oxide materials are examined. A simplified model for the surface-initiated radical oxidation chemistry pathways, was then used to probe a selectivity descriptor based on the different reactivities of propyl radicals. Using this knowledge, we design, and test model 3D printed BN based monoliths that optimize homogeneous reaction pathways. These catalysts are shown to be highly active and selective and stable for ~2.5wks. The results also suggest that oxygenates may be relevant products from homogeneous reactions. "The Boron Project," as we so lovingly called it, has seen several PhD students matriculate as we contributed diligently to uncovering the behavior of this material. The goal of this work is to highlight new avenues through which we can further understand surface reactivity, new tools through which we can probe gas phase radical chemistries, and new catalyst design approaches.

Download or read book Metal Oxides in Heterogeneous Catalysis written by Jacques C. Vedrine and published by Elsevier. This book was released on 2018-01-11 with total page 620 pages. Available in PDF, EPUB and Kindle. Book excerpt: Metal Oxides in Heterogeneous Catalysis is an overview of the past, present and future of heterogeneous catalysis using metal oxides catalysts. The book presents the historical, theoretical, and practical aspects of metal oxide-based heterogeneous catalysis. Metal Oxides in Heterogeneous Catalysis deals with fundamental information on heterogeneous catalysis, including reaction mechanisms and kinetics approaches.There is also a focus on the classification of metal oxides used as catalysts, preparation methods and touches on zeolites, mesoporous materials and Metal-organic frameworks (MOFs) in catalysis. It will touch on acid or base-type reactions, selective (partial) and total oxidation reactions, and enzymatic type reactions The book also touches heavily on the biomass applications of metal oxide catalysts and environmentally related/depollution reactions such as COVs elimination, DeNOx, and DeSOx. Finally, the book also deals with future trends and prospects in metal oxide-based heterogeneous catalysis. - Presents case studies in each chapter that provide a focus on the industrial applications - Includes fundamentals, key theories and practical applications of metal oxide-based heterogeneous catalysis in one comprehensive resource - Edited, and contributed, by leading experts who provide perspectives on synthesis, characterization and applications

Download or read book Investigation of Active Site Structure and Formation on Boron based Oxidative Dehydrogenation Catalysts written by Melissa Cendejas and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Light olefins such as propylene and ethylene are the two most important building blocks in the chemical industry, and their production is energetically costly. Oxidative dehydrogenation (ODH) of light alkanes has been studied as a lower energy alternative method to produce light olefins. Despite decades of research, there has yet to be a catalyst that is selective and productive enough for industrial implementation. Boron containing materials have recently been identified as highly selective catalysts for the ODH of light alkanes to olefins. These materials, such as hexagonal boron nitride (h-BN), exhibit higher propylene selectivity compared to the previous state-of-the-art supported vanadium oxide catalysts (90% propylene selectivity for h-BN vs. 70% for V/SiO2 at 4% propane conversion). Our group's previous work on these catalysts revealed that the reaction proceeds via a gas-phase radical mechanism, presumably initiated by the surface, and that dynamic boron oxy/hydroxy layer is responsible for catalytic activity. The dynamic nature of the active surface prevents the precise definition of an active site using ex situ techniques. In this work, I describe the use of controlled synthesis and detailed solid state NMR characterization to probe the requirements for active site formation on the catalyst surface. I also describe the first set of in situ/operando X-ray spectroscopy studies of propane ODH over hBN. Operando X-ray Raman spectroscopy is used to show the changes that occur to the catalyst on a bulk scale, while in situ near ambient pressure X-ray photoelectron spectroscopy reveals the near-surface of the catalyst during propane ODH. The X-ray spectroscopy measurements described set the foundation for future studies of the working catalyst.

Download or read book The Activation of Dioxygen and Homogeneous Catalytic Oxidation written by D.H.R. Barton and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 503 pages. Available in PDF, EPUB and Kindle. Book excerpt: This monograph consists of the proceedings of the Fifth International Symposium on the Activation of Dioxygen and Homogeneous Catalytic Oxidation, held in College Station, Texas, March 14-19, 1993. It contains an introductory chapter authored by Professors D. H. R. Barton and D. T. Sawyer, and twenty-nine chapters describing presentations by the plenary lecturers and invited speakers. One of the invited speakers, who could not submit a manuscript for reasons beyond his control, is represented by an abstract of his lecture. Also included are abstracts of forty-seven posters contributed by participants in the symposium. Readers who may wish to know more about the subjects presented in abstract form are invited to communicate directly with the authors of the abstracts. This is the fifth international symposium that has been held on this subject. The first was hosted by the CNRS, May 21-29, 1979, in Bendor, France (on the Island of Bandol). The second meeting was organized as a NATO workshop in Padova, Italy, June 24-27, 1984. This was followed by a meeting in Tsukuba, Japan, July 12-16, 1987. The fourth symposium was held at Balatonfured, Hungary, September 10-14, 1990. The sixth meeting is scheduled to take place in Delft, The Netherlands (late Spring, 1996); the organizer and host will be Professor R. A. Sheldon.

Download or read book Development of Boron based Catalysts for the Oxidation of Light Alkanes to Olefins written by William Peter McDermott and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The production of light olefins, such as ethylene and propylene, is a key pillar of the chemical industry as they can be transformed into oxygenates, polymers, and other specialty chemicals. Traditionally, these light olefins have been produced through the steam cracking of petroleum-derived feedstocks. In recent years, the wide availability of natural gas has made light olefin production from light alkanes economically advantageous. However, the current routes to light olefins from natural gas are inefficient, with both steam cracking and non-oxidative alkane dehydrogenation suffering from high reaction temperatures and coke deposition. This has driven academic and industrial research into oxidative alternatives such as the oxidative dehydrogenation (ODH) of alkanes to olefins. Catalysts such as supported vanadium oxides have been studied for the ODH of propane where kinetic and mechanistic studies have led to improvements in this system. However, despite decades of research, work in this area has still not delivered a catalyst with sufficient light olefin selectivity for industrial use.This thesis presents the discovery and development of hexagonal boron nitride (hBN) as a selective catalyst for the ODH of propane and other light alkanes. This material offers superior light olefin selectivity and reduced CO and CO2 selectivity when compared to previously studied metal oxide catalysts. Through kinetic insights, I will show that hBN activates oxygen and alkanes in a manner that is fundamentally different than metal oxides. Spectroscopic characterization shows that the surface of hBN oxidizes to form a BOx layer after exposure to reaction conditions. It is this discovery that led to the establishing of a new class of selective ODH catalysts: elemental boron and inorganic borides. The investigation of the reactivity and structure of these materials offers additional information concerning the origin of activity of boron-containing catalysts. Alongside evaluating the origin of reactivity of these promising ODH catalysts, attention was given to the oxidative cracking of hydrocarbons. Within our initial studies of hBN, we had observed that low PO2 conditions enhanced the selectivity to light olefins. However, these conditions also lead to low alkane conversions. Using n-butane as a model substrate, we optimized the reaction conditions to enhance conversion and light olefin selectivity. Here, we demonstrate that this system is one of the most selective for oxidative cracking. This study also offers further insight into the role of O2 and provides evidence for a surface-initiated gas phase radical mechanism. This thesis culminates with the latest findings in probing the gas phase reactivity of boron-based ODH catalysts. We observe enhanced rates with the dilution of catalyst, providing further evidence for a gas phase mechanism. Alongside these reactivity studies, spectroscopic insights reveal the role of agglomerated BOx formation in ODH reactivity. Also presented here is an outlook on the future study of boron-based catalysts for alkane oxidations and the targeted studies required for continued development of this promising system.

Download or read book Solid State Surface and Catalytic Studies of Oxides written by and published by . This book was released on 2004 with total page 5 pages. Available in PDF, EPUB and Kindle. Book excerpt: This project investigates the catalytic properties of oxides for the selective oxidative dehydrogenation of light alkanes and for hydrocarbon reduction of NO(subscript x). Various vanadium oxide based catalysts were investigated to elucidate the relationship between the chemical and structural properties of the catalysts and their selectivity for the formation of alkenes. It was found that vanadium oxide units that are less reducible give higher selectivities. For hydrocarbon reduction of NO(subscript x), it was found that alumina-based catalysts can be effective at higher temperatures than the corresponding zeolite-based catalysts. On some catalysts, such as SnO2/Al2O3. Ag/Al2O3, the alumina participates directly in the reaction, making the catalyst bifunctional. These results are useful in research to improve the performance of this stress of catalysts.

Download or read book Natural Gas Conversion VI written by T.H. Fleisch and published by Elsevier. This book was released on 2001-06-01 with total page 577 pages. Available in PDF, EPUB and Kindle. Book excerpt: This volume contains peer-reviewed manuscripts describing the scientific and technological advances presented at the 6th Natural Gas Conversion Sumposium held in Alaska in June 2001. This symposium continues the tradition of excellence and the status as the premier technical meeting in this area established by previous meetings.The 6th Natural Gas Conversion Symposium is conducted under the overall direction of the Organizing Committee. The Program Committee was responsible for the review, selection, editing of most of the manuscripts included in this volum. A standing International Advisory Board has ensured the effective long-term planning and the continuity and technical excellence of these meetings.

Download or read book Catalytic Oxidative Dehydrogenation of Ethane written by Shannon L. Lashbrook and published by . This book was released on 2001 with total page 68 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Catalytic Activation and Functionalisation of Light Alkanes written by E.G. Derouane and published by Springer Science & Business Media. This book was released on 2013-11-11 with total page 482 pages. Available in PDF, EPUB and Kindle. Book excerpt: Light alkanes tend to be resistant to many forms of activation. The horizontal approach of the present book covers homogeneous, heterogeneous and biological catalysis, thus allowing readers to gain an awareness of progress and ideas in research areas different from their own. The book contains both general chapters, giving an overview of the subject, and specialised contributions that deal with the details and state of the art. A specialist report is also included which gives a critical insight into current progress and discusses future prospects and major challenges. Audience: Newcomers and senior researchers in the field of alkane activation. The mixed theoretical and practical approach will be of interest to researchers and industrialists alike.