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Table Of Contents

1.1 INTRODUCTION
1.2 INDUSTRIAL CATALYSIS
1.2.1 Sulphuric Acid
1.2.2 Ammonia Synthesis
1.2.4 Catalytic Reforming
1.2.5 Hydrorefining
1.2.6 Acetaldehyde
1.2.7 Butanol
1.2.8 Acetic Acid
1.2.9 Polymerization
1.2.10 Metathesis
1.2.12 Motor Vehicle Emission Control
1.3 SUMMARY
2.5 CATALYSTS FOR AUTOMOTIVE POLLUTION CONTROL
2.6 ETHENE OXIDE
2.7 STYRENE AND PROPYLENE OXIDE (SMPO PROCESS)
2.8 HIGHER OLEFINS
2.9 RHODIUM CATALYZED HYDROFORMYLATION OF PROPENE
2.10 METHANOL SYNTHESIS
2.11 MALEIC ANHYDRIDE
2.14 VITAMIN A INTERMEDIATES
2.15 IBUPROFEN
3.1 INTRODUCTION
3.2 RATE EXPRESSION (SINGLE SITE MODEL)
3.3 RATE DETERMINING STEP - QUASI-EQUILIBRIUM
3.3 ADSORPTION ISOTHERMS
3.4 RATE EXPRESSION (OTHER MODELS)
3.5 INITIAL RATE EXPRESSIONS
3.6 TEMPERATURE DEPENDENCY - LIMITING CASES
3.7 SABATIER PRINCIPLE - VOLCANO PLOT
3.8 CONCLUDING REMARKS
4.1 INTRODUCTION
4.2 BONDING
4.2.1 Bonding to Transition Metal Surfaces
4.3 ELEMENTARY STEPS IN ORGANOMETALLIC COMPLEXES
4.3.1 Creation of a Vacant Site
4.3.2 Coordination of the Substrate
4.3.3 Insertions and Migrations
4.3.4 P-Elimination and Deinsertion
4.3.5 Oxidative Addition
4.3.6 Reductive Elimination
4.3.7 a-Elimination Reactions
4.3.8. Cyclometallation
4.3.9 Activation of a Substrate toward Nucleophilic Attack
4.3.10 a-Bond Metathesis
4.3.22 Heterolytic Cleavage of Dihydrogen
4.4 ELEMENTARY REACTION STEPS ON SURFACES
4.4.1 Metal Catalysed Reactions
4.4.2 Mechanism of the Reactions on Oxides
4.4.3 Catalysis by Solid Acids
5.1 INTRODUCTION
5.2 SYNTHESIS GAS REACTIONS
5.2.1 Introduction
5.2.2 Fischer-Tropsch Synthesis of Hydrocarbons
5.2.4 Related Reactions
5.3 HYDRO-DEHYDROGENATION REACTIONS ON METALS
5.3.1 Introduction
5.3.2 Hydrogenation of Olefins
5.3.3 Reactions of Polyenic and Acetylenic Molecules
5.3.4 Aromatics
5.3.5 Related Reactions
5.3.6 Reactions of Saturated Hydrocarbons
5.4 CATALYTIC OXIDATION
5.4.1 Introduction
5.4.2 Epoxidation of Ethene
6.1 INTRODUCTION
6.2 RHODIUM CATALYZED HYDROFORMYLATION
6.2.1 Introduction
6.2.2 Rhodium-based Hydroformylation
6.2.3 Ligand Effects
6.2.4 Phosphine Ligands
6.2.5 Ligand Efseects in Rhodium Catalyzed Hydroformylation
6.2.6 Kinetic Studies
6.2.7 The Characterization of Intermediates
6.3 ZIRCONIUM CATALYZED POLYMERIZATION OF ALKENES
6.3.1 Introduction
6.3.2 Supported Titanium Catalysts
6.3.3 Isotactic Polypropylene
6.3.4 The Cossee-Adman Mechanism
6.3.5 Homogeneous versus Heterogeneous Catalysts
6.3.6 Site Control versus Chain-end Control
6.3.7 Chain-End Control: Syndiotactic Polymers
6.3.8 Chain-End Control: Isotactic Polymers
6.3.10 Site Control: Isotactic Polymers
6.3.11 Double Stereoselection: Chain-End Control and Site Control
6.3.12 Further Work
6.4 ASYMMETRIC HYDROGENATION
6.4.1 Introduction
6.4.2 Cinnamic Acid Derivatives
6.4.4 BINAP Catalysis
7.1 INTRODUCTION
7.2 MAJOR REACTOR CATEGORIES
7.2.1 Batch Reactor
7.2.2 Plug Flow Reactor
7.2.3 Continuous Flow Stirred Tank Reactor (CSTR)
7.2.4 Nonisothermal Reactors
7.3 REACTION COMBINED WITH TRANSPORT
7.3.1 Heterogeneous Catalysis
7.3.2 Homogeneous Catalysis
7.4 EXPERIMENTAL DETERMINATION OF REACTION KINETICS
7.4.2 Reactors
APPENDIX 7.A: MULTICOMPONENT DIFFUSION IN THE PRESENCE OF REACTION
REFERENCES
8.1 INTRODUCTION
8.2 PREPARATION OF SILICA GEL CATALYST SUPPORTS
8.2.1 Preparation of Silica Gel
8.3. PREPARATION OF ALUMINA CATALYST SUPPORTS
8.3.1 Preparation of y-Al2O3 and q-A1203
8.4 ZEOLITE SYNTHESIS
8.4.1 Introduction
8.4.3 Synthesis of Zeolite Y
8.4.5 Synthesis of ZSM-5
8.5 CATALYST SHAPING
8.5.1 Introduction
8.5.2 Spray Dying
8.5.3 Granulation
8.5.4 Pelletization
8.5.5 Extrusion
8.5.6 Oil-Drop MethodlSol-Gel Method
9.1 INTRODUCTION
9.2 SELECTIVE REMOVAL
9.3 APPLICATION ON A SEPARATELY PRODUCED SUPPORT
9.3.1 Support Surface Chemisty
9.3.2 Impregnation
9.3.3 Deposition-Precipitation
10.2.1 X-Ray Diflraction (XRD)
10.2.2 Electron Microscopy
10.2.3 Temperature Programmed Techniques
10.2.4 Surface Spectroscopy
10.2.5 Infrared Spectroscopy
10.2.6 Extended X-Ray Absovption Fine Structure (EXAFS)
10.2.7 Mossbauer Spectroscopy
10.3 CONCLUDING REMARKS
10.3.1 Research Strategies
11.6 EXAMPLE 2: TEMPERATURE-PROGRAMMED SULPHIDING OF Mo03/A1203
11.7 MODELLING
11.7.1 The0 y
11.7.2 Reduction Kinetic Models
11.7.3 Activation energy
11.7.4 Recommended experimental conditions for TPR
11.8 EXAMPLE 3: MODELLING OF TPR OF Fez03
12.1 INTRODUCTION
12.2 PHYSICAL ADSORPTION
12.6 THE YARDSTICK IN THE DETERMINATION OF SURFACE AREAS
Subject Index
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42792591 Catalysis an Integrated Approach to Homogenous Heterogenous and Industrial Catalysis 044489229X

42792591 Catalysis an Integrated Approach to Homogenous Heterogenous and Industrial Catalysis 044489229X

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Published by Loutfy Madkour
Chapter 1
HISTORY OF CATALYSIS
J.A. Moulljn. P.W.N.M. van Leeuwen and R.A. Santen
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 IndustrialCatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.1 SulphuricAcid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.2 AmmoniaSynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.3 Coal. Oil. Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.4 Catalytic Reforming . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.5 Hydrorefining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.2.6 Acetaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.2.7 Butanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.2.8 AceticAcid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.2.9 Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.2.10 Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.2.11 Motor Vehicle Emission Control . . . . . . . . . . . . . . . . . . 16
1.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Chapter 2
CATALYTIC PROCESSES IN INDUSTRY
J.A. Moulljn. R.A. Sheldon. H . van Bekkum and P.W.N.M. van Leeuwen
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.1 Catalytic Reforming . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.2 Catalytic Processes in the Oil Refinery . . . . . . . . . . . . . . . . . . . 23
2.2.2 Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.3 Hydrotreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.4 Isotactic Polypropylene . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3 Total Isomerization
4.3.4 P-Elimination and Deinsertion . . . . . . . . . . . . . . . . . . .1 11
4.3.5 Oxidative Addition . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.3.6 Reductive Elimination . . . . . . . . . . . . . . . . . . . . . . . . 115
4.3.7 a-Elimination Reactions . . . . . . . . . . . . . . . . . . . . . . .11 6
4.3.8 Cyclometallation . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Activation of a Substrate toward Nucleophilic Attack . . . . . . 120
4.3.10 o-Bond Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . 122
4.3.11 Heterolytic Cleavage of Dihydrogen . . . . . . . . . . . . . . . .1 23
Elementary Reaction Steps on Surfaces . . . . . . . . . . . . . . . . . . 123
4.4.1 Metal Catalysed Reactions . . . . . . . . . . . . . . . . . . . . . . 124
4.4.2 Mechanism of the Reaction on Oxides . . . . . . . . . . . . . . .1 40
4.4.3 Catalysis by Solid Acids . . . . . . . . . . . . . . . . . . . . . . . 143
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
4.3.9
4.4
Chapter 5
HETEROGENEOUS CATALYSIS
J.A. Moulijn and V . Ponec
5.2
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Synthesis Gas Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
5.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Fischer-Tropsch Synthesis of Hydrocarbons . . . . . . . . . . . 160
Promoters and Supports . . . . . . . . . . . . . . . . . . . . . . . 166
5.2.4 Related Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Hydro-Dehydrogenation Reactions on Metals . . . . . . . . . . . . . . 176
5.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Hydrogenation of Olefins . . . . . . . . . . . . . . . . . . . . . . 176
Reactions of Polyenic and Acetylenic Molecules . . . . . . . . . 180
5.3.4 Aromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5.3.5 Related Reactions . . .
Chapter 1
HISTORY OF CATALYSIS
J.A. Moulljn. P.W.N.M. van Leeuwen and R.A. Santen
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 IndustrialCatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.1 SulphuricAcid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.2 AmmoniaSynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.3 Coal. Oil. Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.4 Catalytic Reforming . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.5 Hydrorefining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.2.6 Acetaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.2.7 Butanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.2.8 AceticAcid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.2.9 Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.2.10 Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.2.11 Motor Vehicle Emission Control . . . . . . . . . . . . . . . . . . 16
1.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Chapter 2
CATALYTIC PROCESSES IN INDUSTRY
J.A. Moulljn. R.A. Sheldon. H . van Bekkum and P.W.N.M. van Leeuwen
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.1 Catalytic Reforming . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.2 Catalytic Processes in the Oil Refinery . . . . . . . . . . . . . . . . . . . 23
2.2.2 Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.3 Hydrotreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.4 Isotactic Polypropylene . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3 Total Isomerization
4.3.4 P-Elimination and Deinsertion . . . . . . . . . . . . . . . . . . .1 11
4.3.5 Oxidative Addition . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.3.6 Reductive Elimination . . . . . . . . . . . . . . . . . . . . . . . . 115
4.3.7 a-Elimination Reactions . . . . . . . . . . . . . . . . . . . . . . .11 6
4.3.8 Cyclometallation . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Activation of a Substrate toward Nucleophilic Attack . . . . . . 120
4.3.10 o-Bond Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . 122
4.3.11 Heterolytic Cleavage of Dihydrogen . . . . . . . . . . . . . . . .1 23
Elementary Reaction Steps on Surfaces . . . . . . . . . . . . . . . . . . 123
4.4.1 Metal Catalysed Reactions . . . . . . . . . . . . . . . . . . . . . . 124
4.4.2 Mechanism of the Reaction on Oxides . . . . . . . . . . . . . . .1 40
4.4.3 Catalysis by Solid Acids . . . . . . . . . . . . . . . . . . . . . . . 143
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
4.3.9
4.4
Chapter 5
HETEROGENEOUS CATALYSIS
J.A. Moulijn and V . Ponec
5.2
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Synthesis Gas Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
5.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Fischer-Tropsch Synthesis of Hydrocarbons . . . . . . . . . . . 160
Promoters and Supports . . . . . . . . . . . . . . . . . . . . . . . 166
5.2.4 Related Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Hydro-Dehydrogenation Reactions on Metals . . . . . . . . . . . . . . 176
5.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Hydrogenation of Olefins . . . . . . . . . . . . . . . . . . . . . . 176
Reactions of Polyenic and Acetylenic Molecules . . . . . . . . . 180
5.3.4 Aromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5.3.5 Related Reactions . . .

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Published by: Loutfy Madkour on May 20, 2012
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