The first book to place recent academic developments within the context of real life industrial applications, this is a timely overview of the field of aerobic oxidation reactions in the liquid phase that also illuminates the key challenges that lie ahead. As such, it covers both homogeneous as well as heterogeneous chemocatalysis and biocatalysis, along with examples taken from various industries: bulk chemicals and monomers, specialty chemicals, flavors and fragrances, vitamins, and pharmaceuticals. One chapter is devoted to reactor concepts and engineering aspects of these methods, while another deals with the relevance of aerobic oxidation catalysis for the conversion of renewable feedstock. With chapters written by a team of academic and industrial researchers, this is a valuable reference for synthetic and catalytic chemists at universities as well as those working in the pharmaceutical and fine chemical industries seeking a better understanding of these reactions and how to design large scale processes based on this technology.
Sets the stage for environmentally friendly industrial organic syntheses From basic principles to new and emerging industrial applications, this book offers comprehensive coverage of heterogeneous liquid-phase selective oxidation catalysis. It fully examines the synthesis, characterization, and application of catalytic materials for environmentally friendly organic syntheses. Readers will find coverage of all the important classes of catalysts, with an emphasis on their stability and reusability. Liquid Phase Oxidation via Heterogeneous Catalysis features contributions from an international team of leading chemists representing both industry and academia. The book begins with a chapter on environmentally benign oxidants and then covers: Selective oxidations catalyzed by TS-1 and other metal-substituted zeolites Selective catalytic oxidation over ordered nanoporous metallo-aluminophosphates Selective oxidations catalyzed by mesoporous metal-silicates Liquid phase oxidation of organic compounds by supported metal-based catalysts Selective liquid phase oxidations in the presence of supported polyoxometalates Selective oxidations catalyzed by supported metal complexes Liquid phase oxidation of organic compounds by metal-organic frameworks Heterogeneous photocatalysis for selective oxidations with molecular oxygen All the chapters dedicated to specific types of catalysts follow a similar organization and structure, making it easy to compare the advantages and disadvantages of different catalysts. The final chapter examines the latest industrial applications, such as the production of catechol and hydroquinone, cyclohexanone oxime, and propylene oxide. With its unique focus on liquid phase heterogeneous oxidation catalysis, this book enables researchers in organic synthesis and oxidation catalysis to explore and develop promising new catalytic materials and synthetic routes for a broad range of industrial applications.
The first book to place recent academic developments within the context of real life industrial applications, this is a timely overview of the field of aerobic oxidation reactions in the liquid phase that also illuminates the key challenges that lie ahead. As such, it covers both homogeneous as well as heterogeneous chemocatalysis and biocatalysis, along with examples taken from various industries: bulk chemicals and monomers, specialty chemicals, flavors and fragrances, vitamins, and pharmaceuticals. One chapter is devoted to reactor concepts and engineering aspects of these methods, while another deals with the relevance of aerobic oxidation catalysis for the conversion of renewable feedstock. With chapters written by a team of academic and industrial researchers, this is a valuable reference for synthetic and catalytic chemists at universities as well as those working in the pharmaceutical and fine chemical industries seeking a better understanding of these reactions and how to design large scale processes based on this technology.
Oxidation reactions are an important chemical transformation in both academia and industry. Among the major advances in the field has been the development of catalytic processes, which are not only selective and efficient, but also allow the replacement of common stoichiometric oxidants with molecular oxygen, ideally from air at atmospheric pressure. This results in processes with higher atom efficiency, where water is the only side product in line with the principles of green chemistry. Focusing on the use of molecular oxygen as the terminal oxidant, this book covers recent advances in both heterogeneous and homogeneous systems, with and without metals and on the “taming” of the highly reactive oxygen gas by use of micro-flow reactors and membranes. A useful reference for industrial and academic chemists working on oxidation processes, as well as green chemists.
This book deals with the search for environmentally benign procedures for the oxidation of alcohols and gives an overview of their transition-metal-catalyzed aerobic oxidation.
Safe and selective aerobic oxidation of organic substrates represents a grand challenge in catalysis. The productive utilization of oxygen is key to many, seemingly disparate, systems, for example, enzymatic catalysis, fine chemical production, and energy generation in fuel cells. This thesis describes new methods for carrying out aerobic oxidation in the latter two applications. Fuel cells are a promising technology for generating electrical energy from the energy in chemical bonds. However, the high loadings of Pt needed to catalyze oxygen reduction at the cathode have hindered broad adoption. To address this, a new fuel cell design was developed wherein oxygen reduction is executed off-electrode in an external reactor with non-Pt catalysts, using quinones as electron-proton transfer mediators. This represents the first instance of organic mediator use outside of low-power, enzymatic fuel cells. The latter part of this thesis details the development of new reactors and catalysts for general aerobic alcohol oxidations. Safe execution of aerobic oxidation in the presence of organic solvents is typically achieved by operating below the limiting oxygen concentration with inert diluents. 'Tube in shell' membrane reactors offer an intriguing alternative, permitting passage of O2 from the gas phase into a liquid-phase reaction through semi-permeable membranes. Use of a membrane reactor with inexpensive PTFE tubing enabled alcohol oxidation at rates an order of magnitude higher than previously reported. Heterogeneous catalysts, particularly noble metals such as Pt and Pd, have been extensively studied for alcohol oxidation. However, these catalysts exhibit low rates and limited substrate scopes due to poisoning by excess oxygen or various heterocycles; thus, various species were explored as catalyst 'promoters.' In the oxidative coupling of alcohols and ammonia to make nitriles, the addition of Bi to a Pt catalyst accelerated the rate of alcohol oxidation and enabled high yields with challenging heterocyclic alcohols. Furthermore, the addition of Bi and Te to a Pd catalyst increased the yield and rate for the oxidative coupling of alcohols with methanol to make methyl esters. Collectively, the above work highlights the opportunities for reaction engineering to enable the safe and selective utilization of oxygen in a range of chemistries.
This first book to focus on catalytic processes from the viewpoint of green chemistry presents every important aspect: · Numerous catalytic reductions and oxidations methods · Solid-acid and solid-base catalysis · C-C bond formation reactions · Biocatalysis · Asymmetric catalysis · Novel reaction media like e.g. ionic liquids, supercritical CO2 · Renewable raw materials Written by Roger A. Sheldon -- without doubt one of the leaders in the field with much experience in academia and industry -- and his co-workers, the result is a unified whole, an indispensable source for every scientist looking to improve catalytic reactions, whether in the college or company lab.
This book consists of lectures presented by international authorities in the field, at a course on Oxidation Catalysis organized by the Dutch Research School in Catalysis at Rolduc in June 1994.The material covered spans the whole range of the subject from the fundamental principles of gas and liquid phase oxidations to reactor engineering for industrial processing. The use of catalytic oxidation in both bulk and fine chemicals manufacture and the different types of catalysis — heterogeneous-gas phase, homogeneous-liquid phase and heterogeneous-liquid phase — are discussed. In addition, a few special topics, such as electrocatalytic and high-temperature oxidation are dealt with.The book is intended for graduate students or industrial researchers who wish to acquaint themselves with the underlying principles of catalytic oxidations and the numerous applications of this important technology.
Volume 1 covers the most important technological aspects of the use of molecular oxygen for catalytic oxidation reactions.Volume 2 addresses the safety issues associated with the use of oxygen in catalytic oxidation reactions.Contents Vol. 1: 1. Introduction. 2. Chemical-physical properties of molecular oxygen. 3. Oxygen production technologies. 4. Chemical fundamentals of oxidation reactions. 5. Reactor technologies for multiphase systems. 6. Liquid phase oxidations. 7. Gas phase selective oxidations. 8. Selective oxidation of paraffins. References. Index. Vol. 2: 9. Introduction to safety problems in the chemical industry. 10. Chemical aspects of combustion in the gaseous phase. 11. Homogeneous chemical explosions: autoignition or spontaneous ignition. 12. Deflagration or propagation of flame. 13. Conditions governing flame propagation capability. 14. Detonation in the gaseous phase. 15. Prevention of and protection against explosions. References. Index.
This book offers a comprehensive overview of the most recent developments in both total oxidation and combustion and also in selective oxidation. For each topic, fundamental aspects are paralleled with industrial applications. The book covers oxidation catalysis, one of the major areas of industrial chemistry, outlining recent achievements, current challenges and future opportunities. One distinguishing feature of the book is the selection of arguments which are emblematic of current trends in the chemical industry, such as miniaturization, use of alternative, greener oxidants, and innovative systems for pollutant abatement. Topics outlined are described in terms of both catalyst and reaction chemistry, and also reactor and process technology.
