Oxychlorination

Abstract: Preface 1 General Introduction 1.1 Presentation of Material 1.2 The Role and Importance of Heterogeneous Catalytic Oxidation Processes in the Chemical Industry References to Chapter 1 2 Introduction to Heterogeneous Catalysis 2.1 Macroscopic and Microscopic Structure of Heterogeneous Catalysts 2.2 The Five Basic Steps in Heterogeneous Catalysis 2.3 Testing of Heterogeneous Catalysts 2.4 Diffusion 2.5 Adsorption at the Gas--Solid Interface 2.6 Kinetics of Oxidation Reactions 2.7 Characterization of Oxidation Catalysts References to Chapter 2 3 General Principles of Heterogeneous Catalytic Oxidation 3.1 Generic Features of Catalytic Oxidation Reactions 3.2 The Mode of Activation of the Hydrocarbon and Discriminating Capacity of Active Sites in Oxidation Catalysis 3.3 Types of Active Oxygen Species Involved in Oxidation Catalysis 3.4 Structural Features of Oxidation Catalysts References to Chapter 3 4 Propene Oxidation to Acrolein: Allylic Oxidation over Catalysts with Highly Mobile Oxygen Anions 4.1 Introduction 4.2 The Composition of Multicomponent Bismuth Molybdate Catalysts for Propene Oxidation 4.3 The Surface Allyl Species 4.4 Source of Oxygen Inserted into Propene to Form Acrolein 4.5 Oxygen Transport within Bismuth Molybdate Catalysts 4.6 The Overall Reaction Mechanism References to Chapter 4 5 Oxidation Activation of Alkanes: Oxidation of n--butane to Maleic Arthydride 5.1 Introduction 5.2 Technologies for the Production of Maleic Anhydride 5.3 The Preparation, Structure and Performance of Vanadium Phosphorus Oxide Catalysts 5.4 Activation of n--butane 5.5 The Nature of the Active Site and the Reaction Mechanism 5.6 Conclusions References to Chapter 5 6 Epoxidation of Alkenes: Reactivity of Electrophilie Oxygen Species 6.1 Introduction 6.2 Technology for Ethylene Oxide Production 6.3 Catalyst Composition, Structure and Performance 6.4 Reaction Kinetics and Network 6.5 The Nature of the Oxygen Species on and under the Silver Surface 6.6 Reactivity of Oxygen Species on Silver References to Chapter 6 7 Catalytic Combustion 7.1 Introduction 7.2 Environmental Applications of Catalytic Combustion 7.3 Principles of Catalytic Combustion 7.4 Choice of Materials for the Construction of Combustion Catalysts 7.5 Poisoning of Combustion Catalysts 7.6 Reactivity of the Substrate 7.7 Kinetics of Catalytic Combustion Reactions 7.8 Nature of the Active Species of Working Precious Metal Catalysts References to Chapter 7 8 Activation and Insertion of Nitrogen into Organic Compounds 8.1 Introduction 8.2 Technology for Propene Ammoxidation 8.3 Catalysts Used in Ammoxidation 8.4 The Ammoxidation Reaction Network 8.5 Mechanism of Nitrogen Insertion in Ammoxidation 8.6 Nitrogen Insertion in Ammoxidation References to Chapter 8 9 Catalytic Oxidation Reactions Involving Chlorine: Oxychlorination and the Oxidative Destruction of Chlorinated Hydrocarbons 9.1 Introduction 9.2 Vinyl Chloride by Oxychlorination 9.3 Technology for Vinyl Chloride Production 9.4 Oxychlorination Catalyst Composition, Preparation and Characterization 9.5 The Mechanism of Oxychlorination 9.6 Destruction of Chlorinated Hydrocarbons by Catalytic Oxidation 9.7 By--product Formation during the Catalytic Oxidation of Chlorinated Hydrocarbons 9.8 Polychlorinated Biphenyls, Dioxins and the Environment References to Chapter 9 10 Oxidation Reactions Catalysed by Zeolites and Structured Mesoporous Materials 10.1 Zeolites 10.2 Redox Molecular Sieves 10.3 Structured Mesoporous Silicates in Oxidation Reactions References to Chapter 10 Index

Abstract: Monochlorophenols are smoothly oxidized to carbon dioxide and carbon monoxide when vapors in air are passed over fixed beds of municipal waste incinerator fly ash at 625-725 K. Simultaneously polychlorinated benzenes, monobenzofurans, and dibenzo-p-dioxins are formed with a large fraction of the original chlorine concentrated in these products. Fly ash catalyzed oxychlorination of phenol in the presence of HCl at 425-725 K resulted in the formation of chlorinated phenols which, in turn, were converted above 625 K into mainly CO 2 and the (poly)chloroarenes mentioned above. In contrast, under similar conditions, (chlorinated) benzenes are inert

Abstract: We have demonstrated that a polyfluorinated alcohol, 2,2,2-trifluoroethanol, solvent enables haloperoxidase type activity and the oxychlorination of arenes (benzene and its alkylated derivatives) without a metal catalyst. The polyfluorinated alcohol has a dual function; it catalyzes electrophilic chlorination of less reactive arenes by several orders of magnitude and oxidation of chloride at lower H+ concentrations. DFT calculations show that a complementary charge template in the transition state explains the catalysis of the electrophilic chlorination.