The Chemistry of the Catalyzed Hydrogenation of Carbon Monoxide

ISBN-13: 9783642696640 / Angielski / Miękka / 2011 / 232 str.

G. Henrici-Olive; S. Olive

Opis

During the oil embargo, in the winter 1973174, parts of Western Europe present ed an almost war-like aspect on Saturdays and Sundays: no traffic on the high ways, no crowds at ski resorts and other weekend entertainment places, no gaso line at the pumps. Living and teaching then in that part of the world, and discussing the situa tion with our students, we came to the conclusion that it would be timely to col lect the fine chemistry already known at the time in the field of conversion of coal to gasoline and other chemicals, and by this way help to draw the attention to this important alternative to crude oil. The idea of this book was born. The energy shock of the early seventies has been healthy and of great conse quences in chemistry. Large amounts of research money have been put to work since, and our knowledge of the possibilities and limitations of coal-based chemistry has increased enormously. During several years it appeared inap propriate to write a monograph about a topic which was in the midst of such an impetuous development. Nevertheless, we collected, and critically selected, the upcoming work as it appeared in the literature, and also tried to provide some modest input ourselves. Now, ten years later, the situation seems to be settled to a certain degree."

Spis treści

1 Introduction.- 1.1 References.- 2 Transition Metal-Hydrogen Interactions.- 2.1 Reaction of Hydrogen with Transition Metal Complexes and Surfaces.- 2.2 Metal-Hydrogen Bond Energy.- 2.3 Different Types of Metal-Hydrogen Bonding and the M-H Bond Length.- 2.4 Polarity of the M-H Bond.- 2.5 Mobility of Hydrogen Ligands.- 2.6 Conclusion.- 2.7 References.- 3 Transition Metal-Carbon Monoxide Interactions.- 3.1 The CO Molecule.- 3.2 Coordination Chemistry of CO in Molecular Complexes and Clusters.- 3.3 Molecular Carbon Monoxide on Metal Surfaces.- 3.4 CO Dissociation on Metal Surfaces.- 3.5 Conclusion.- 3.6 References.- 4 Non-Catalytic Interaction of CO with H2.- 4.1 On Metal Surfaces.- 4.2 CO/H2 Interaction in Transition Metal Complexes.- 4.2.1 Hydridocarbonyl Complexes.- 4.2.2 Formyl Complexes.- 4.2.3 Formaldehyde Complexes.- 4.2.4 A Methoxy Complex.- 4.2.5 Carbide Complexes.- 4.3 Conclusions.- 4.4 References.- 5 Key Reactions in Catalysis.- 5.1 Oxidative Addition.- 5.2 Reductive Elimination.- 5.2.1 Intramolecular Reductive Elimination.- 5.2.2 Intermolecular Reductive Elimination.- 5.3 Migratory Insertion Reactions.- 5.3.1 CO Insertion into Metal-Alkyl Bonds.- 5.3.2 Alkyl Migration versus CO Migration.- 5.3.3 Promotion of Migratory CO Insertion.- 5.3.4 Absence of Acyl-to-CO Migration.- 5.3.5 CO Insertion into Metal-H Bonds.- 5.3.6 Migratory Insertions involving Carbene Ligands.- 5.3.7 Olefin Insertion.- 5.3.8 Coinsertion of Ethylene and CO.- 5.3.9 Insertion of Formaldehyde.- 5.4 Hydrogen Eliminiation Reactions.- 5.4.1 ?-Hydrogen Elimination.- 5.4.2 ?-Elimination of Hydrogen.- 5.4.3 ?- and ?-Elimination of Hydrogen.- 5.5 Ligand Influences.- 5.5.1 In Molecular Complexes.- 5.5.2 On Metal Surfaces.- 5.6 Conclusion.- 5.7 References.- 6 Catalysts and Supports.- 6.1 Molecular Complexes and Metal Surfaces — Analogies and Differences.- 6.2 Supported Metal Catalysts.- 6.2.1 Metals and Supports Used for CO Hydrogenation.- 6.2.2 Metal-Support Interactions.- 6.2.3 Steric Constraints in Zeolites.- 6.3 Conclusions.- 6.4 References.- 7 Methanation.- 7.1 Carbide Mechanism.- 7.2 CO Insertion Mechanism.- 7.3 Inverse H/D Isotope Effects.- 7.4 Conclusion.- 7.5 References.- 8 Methanol from CO + H2.- 8.1 Nondissociative Incorporation of CO.- 8.2 Homogeneous Methanol Formation.- 8.3 Methanol Synthesis with Supported Noble Metal Catalysts.- 8.4 Synergism in the Cu/ZnO Catalyst.- 8.5 Conclusions.- 8.6 References.- 9 Fischer-Tropsch Synthesis.- 9.1 Early Developments and Present State of Commercial Fischer-Tropsch Synthesis.- 9.2 The Products of the FT Synthesis.- 9.2.1 Primary Products.- 9.2.2 Secondary Reactions of the ?-Olefins.- 9.2.3 Modified FT Synthesis.- 9.3 Distribution of Molecular Weights.- 9.3.1 The Schulz-Flory Distribution Function.- 9.3.2 Experimental Molecular Weight Distributions.- 9.4 Kinetics and Thermodynamics of the FT Reaction.- 9.5 Reaction Mechanism.- 9.5.1 Suggested Mechanisms.- 9.5.2 The Carbide Theory in the Light of Homogeneous Coordination Chemistry.- 9.5.3 Details and Support for the CO Insertion Mechanism.- 9.5.4 The Chain Initiating Step.- 9.5.5 Secondary Reactions.- 9.6 Influence of the Dispersity of Metal Centers.- 9.7 Influence of the Temperature and Pressure.- 9.7.1 Hydrocarbons versus Oxygenates.- 9.7.2 The Particular Case of Ruthenium Catalysts.- 9.8 The Role of Alkali Promoters.- 9.9 Product Selectivity.- 9.9.1 Consequences of the Schulz-Flory Molecular Weight Distribution.- 9.9.2 Deviations from the Schulz-Flory Distribution.- 9.10 Conclusion.- 9.11 References.- 10 Homogeneous CO Hydrogenation.- 10.1 Hydroformylation of Olefins (Oxo Reaction).- 10.2 Hydroformylation of Formaldehyde.- 10.3 Polyalcohols from CO + H2, and Related Homogeneous Syntheses.- 10.4 Conclusion.- 10.5 References.- 11 Methanol as Raw Material.- 11.1 Carbonylation of Methanol (Acetic Acid Synthesis)..- 11.2 Methanol Homologation.- 11.3 Hydrocarbons from Methanol Dehydration and Condensation.- 11.4 Conclusion.- 11.5 References.- 12 Attempt of a Unified View.- 12.1 References.- 13 Subject Index.