Homogeneous Catalysis: Mechanisms and Industrial Applications / Edition 1

Homogeneous Catalysis: Mechanisms and Industrial Applications / Edition 1

by Sumit Bhaduri, Doble Mukesh
     
 

This timely book responds to the need in the chemical industry for a guidebook devoted to the key concepts of homogeneous catalysis. Focusing on homogeneous catalytic reactions with proven industrial applications, this practical work helps industrial chemists bridge the gap between imaginative academic research and successful technology. See more details below

Overview

This timely book responds to the need in the chemical industry for a guidebook devoted to the key concepts of homogeneous catalysis. Focusing on homogeneous catalytic reactions with proven industrial applications, this practical work helps industrial chemists bridge the gap between imaginative academic research and successful technology.

Product Details

ISBN-13:
9780471372219
Publisher:
Wiley
Publication date:
03/13/2000
Edition description:
New Edition
Pages:
256
Product dimensions:
6.50(w) x 9.53(h) x 0.94(d)

Table of Contents

Prefacexiii
1Chemical Industry and Homogeneous Catalysis1
1.1Feed Stocks and Definitions1
1.2Feed Stock to Basic Building Blocks by Heterogeneous Catalysis2
1.3Basic Building Blocks to Downstream Products by Homogeneous Catalysis4
1.4Comparison Among Different Types of Catalysis5
1.5What Is To Follow--A Summary8
Problems10
Bibliography11
2Basic Chemical Concepts13
2.1The Metal13
2.1.1Oxidation State and Electron Count13
2.1.2Coordinative Unsaturation15
2.1.3Rare Earth Metals17
2.2Important Properties of Ligands17
2.2.1CO, R[subscript 2]C=CR[subscript 2], PR[subscript 3], and H[superscript -] as Ligands17
2.2.2Alkyl, Allyl, and Alkylidene Ligands18
2.3Important Reaction Types19
2.3.1Oxidative Addition and Reductive Elimination19
2.3.2Insertion Reactions22
2.3.3[beta]-Hydride Elimination23
2.3.4Nucleophilic Attack on a Coordinated Ligand23
2.4Energy Considerations--Thermodynamics and Kinetics25
2.5Catalytic Cycle and Intermediates25
2.5.1Kinetic Studies28
2.5.2Spectroscopic Studies29
2.5.3Model Compounds and Theoretical Calculations30
Problems33
Bibliography35
3Chemical Engineering Fundamentals37
3.1Reactor Design37
3.1.1Stirred Tank Reactors39
3.1.2Tubular Reactors41
3.1.3Membrane Reactors42
3.1.4Construction Materials43
3.2Operating Conditions43
3.3Mass Transfer in Multiphase Reactions44
3.4Heat Transfer45
3.5Catalyst Recovery46
3.6Unit Operations47
3.6.1Crystallization and Filtration47
3.6.2Distillation47
3.6.3Liquid-Liquid Extraction49
3.6.4Gas-Liquid Absorption (or Scrubbing)50
3.7Safety Aspects50
3.8Effluent and Waste Disposal51
3.9Economics51
Problems52
Bibliography54
4Carbonylation55
4.1Introduction55
4.2Manufacture of Acetic Acid56
4.2.1The Monsanto Process--The Catalytic Cycle56
4.2.2Mechanistic Studies and Model Compounds59
4.2.3The BASF Process--The Catalytic Cycle60
4.2.4BASF Process--Mechanistic Studies61
4.3Water-Gas Shift Reaction and Rhodium-Catalyzed Carbonylation62
4.4Fischer-Tropsch Reaction and Cobalt-Catalyzed Carbonylation64
4.5Rhodium-Catalyzed Carbonylation of Other Alcohols66
4.6Carbonylation of Methyl Acetate68
4.6.1Mechanism and Catalytic Cycle69
4.7Carbonylation of Alkynes; Manufacture of Methyl Methacrylate70
4.7.1Mechanism and Catalytic Cycle71
4.8Other Carbonylation and Hydrocarboxylation Reactions74
4.9Engineering Aspects77
Problems79
Bibliography82
5Hydroformylation85
5.1Background85
5.2The Rhodium Process86
5.2.1The Catalytic Cycle86
5.2.2Product Selectivity88
5.2.3Mechanistic Studies88
5.2.4The Phosphorus Ligands and Selectivity90
5.2.5Water-Soluble Phosphines and Rhodium Recovery92
5.2.6Catalyst and Ligand Degradation95
5.3Cobalt-Based Hydroformylation96
5.4Other Hydroformylation Reactions98
5.5Engineering Aspects99
Problems99
Bibliography102
6Polymerization105
6.1Introduction105
6.1.1Polyethylene105
6.1.2Polypropylene106
6.2Catalysts for Polyethylene107
6.3Catalysts for Polypropylene108
6.4Catalytic Cycle for Alkene Polymerization109
6.4.1Cossee-Arlman Mechanism109
6.4.2Mechanism of Alkene Insertion111
6.4.3Mechanistic Evidence113
6.5Metallocene Catalysts113
6.5.1Structures of Metallocene Catalysts and the Co-catalysts114
6.5.2Special Features and Advantages of Metallocene Catalysts118
6.5.3Mechanism of Polymerization and Stereocontrol by Metallocene Catalysts119
6.6Chromocene and Heterogeneous Catalysts123
6.7Polymers of Other Alkenes125
6.8Engineering Aspects125
Problems127
Bibliography130
7Other Alkene-Based Homogeneous Catalytic Reactions133
7.1Introduction133
7.2Isomerization of Alkenes133
7.2.1Catalytic Cycle134
7.3Hydrogenation of Alkenes135
7.3.1Catalytic Cycle136
7.3.2Mechanistic Evidence137
7.4Oligomerization of Ethylene138
7.4.1Shell Higher Olefin Process139
7.5Di-, Tri-, and Codimerization Reactions142
7.5.1Dimerization of Propylene142
7.5.2Di- and Trimerization of Butadiene142
7.5.3Dimerization of Butadiene with Ethylene147
7.6Metathesis Reactions147
7.6.1Mechanistic Studies147
7.7Hydrocyanation151
7.7.1Catalysts for Hydrocyanation153
7.7.2Catalytic Cycle for the First Stage154
7.7.3Catalytic Cycle for the Second Stage156
7.8Hydrosilylation159
7.8.1Catalytic Cycle and Mechanism160
7.9C-C Coupling and Cyclopropanation Reactions161
7.9.1Catalytic Cycle for the Heck Reaction163
7.9.2Catalytic Cycle for Cyclopropanation163
Problems165
Bibliography168
8Oxidation171
8.1Introduction171
8.2Wacker Oxidation172
8.2.1The Background Chemistry173
8.2.2Catalytic Cycle and Mechanism174
8.3Metal-Catalyzed Liquid-Phase Autoxidation176
8.3.1Mechanism of Autoxidation177
8.3.2Special Features of Cyclohexane Oxidation179
8.3.3Special Features of p-Xylene Oxidation181
8.4Polymers (Polyesters and Polyamides) from Autoxidation Products182
8.5Epoxidation of Propylene183
8.5.1Catalytic Cycle and the Mechanism of Propylene Epoxidation184
8.6Oxo Complexes as Homogeneous Oxidation Catalysts186
8.6.1Mechanism of Oxidation by Oxo Compounds187
8.7Engineering and Safety Considerations188
Problems190
Bibliography193
9Asymmetric Catalysis195
9.1Introduction195
9.2General Features of Chiral Ligands and Complexes196
9.3Mechanisms and Catalytic Cycles202
9.3.1Mechanism of Asymmetric Hydrogenation203
9.3.2Asymmetric Isomerization and Mechanism207
9.3.3Asymmetric Epoxidation of Allylic Alcohols and Mechanisms209
9.3.4Asymmetric Epoxidation of Alkenes other than Allyl Alcohols211
9.3.5Asymmetric Hydrolysis of Epoxides212
9.4Asymmetric Dihydroxylation Reaction215
9.4.1Mechanism of ADH Reaction216
9.5Asymmetric Catalytic Reactions of C-C Bond Formation217
9.5.1Asymmetric Hydroformylation Reaction218
9.5.2Mechanism of Asymmetric Hydroformylation Reaction221
9.5.3Asymmetric Hydrocyanation Reaction223
9.5.4Nitroaldol Condensation225
Problems227
Bibliography231
Index233

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