Table of Contents

Cover

Related Titles

Title Page

Preface to the Third Edition

Abbreviations

Chapter 1: Introduction

1.1 The Phenomenon Catalysis
1.2 Mode of Action of Catalysts
1.3 Classification of Catalysts
1.4 Comparison of Homogeneous and Heterogeneous Catalysis
Exercises
References

Chapter 2: Homogeneous Catalysis with Transition Metal Catalysts

2.1 Key Reactions in Homogeneous Catalysis
2.2 Catalyst Concepts in Homogeneous Catalysis
2.3 Characterization of Homogeneous Catalysts
Exercises
References

Chapter 3: Homogeneously Catalyzed Industrial Processes

3.1 Overview
3.2 Examples of Industrial Processes
3.3 Asymmetric Catalysis
3.4 Alkene Metathesis
3.5 Recycling of Homogeneous Catalysts
Exercises
References

Chapter 4: Biocatalysis

4.1 Introduction
4.2 Kinetics of Enzyme-Catalyzed Reactions
4.3 Industrial Processes with Biocatalysts
Exercises
References

Chapter 5: Heterogeneous Catalysis: Fundamentals

5.1 Individual Steps in Heterogeneous Catalysis
5.2 Kinetics and Mechanisms of Heterogeneously Catalyzed Reactions
5.3 Catalyst Concepts in Heterogeneous Catalysis
5.4 Catalyst Performance
5.5 Catalyst Deactivation
5.6 Regeneration and Recycling of Heterogeneous Catalysts
5.7 Characterization of Heterogeneous Catalysts
Exercises
References

Chapter 6: Catalyst Shapes and Production of Heterogeneous Catalysts

6.1 Introduction
6.2 Bulk Catalysts
6.3 Supported Catalysts
6.4 Shaping of Catalysts and Catalyst Supports
6.5 Immobilization of Homogeneous Catalysts
Exercises
References

Chapter 7: Shape-Selective Catalysis: Zeolites

7.1 Composition and Structure of Zeolites
7.2 Catalytic Properties of the Zeolites
7.3 Isomorphic Substitution of Zeolites
7.4 Metal-Doped Zeolites
7.5 Applications of Zeolites
Exercises
References

Chapter 8: Heterogeneously Catalyzed Processes in Industry

8.1 Overview
8.2 Examples of Industrial Processes – Bulk Chemicals
8.3 Fine Chemicals Manufacture
Exercises
References

Chapter 9: Refinery Processes and Petrochemistry

9.1 Hydrotreating
9.2 Catalytic Cracking
9.3 Hydrocracking
9.4 Catalytic Reforming
9.5 Alkylation
9.6 Hydroisomerization
9.7 Synthesis Gas and Hydrogen by Steam Reforming
9.8 Natural Gas Conversion to Fuels and Chemicals
9.9 Fischer–Tropsch Synthesis
9.10 Etherification Reactions
Exercises
References

Chapter 10: Electrocatalytic Processes

10.1 Comparison Between Electrocatalysis and Heterogeneous Catalysis
10.2 Electroorganic Syntheses
10.3 Electrocatalysis in Fuel Cells
Exercises
References

Chapter 11: Environmental Catalysis and Green Chemistry

11.1 Automotive Exhaust Catalysis
11.2 NO_x Removal Systems
11.3 Catalytic Afterburning
11.4 Green Chemistry and Catalysis
Exercises
References

Chapter 12: Phase-Transfer Catalysis

12.1 Definition
12.2 Catalysts for PTC
12.3 Mechanism and Benefits of PTC
12.4 PTC Reactions
12.5 Selected Industrial Processes with PTC
Exercises
References

Chapter 13: Catalytic Processes with Renewable Materials

13.1 Biofuels
13.2 Biorefinery
13.3 Chemicals from Biomass
Exercises
References

Chapter 14: Polymerization Catalysis

14.1 Introduction
14.2 Fundamentals of Catalytical Polymerization Processes
14.3 Coordination Polymerization
14.4 Examples of Catalytical Polymerization Processes
Exercises
References

Chapter 15: Planning, Development, and Testing of Catalysts

15.1 Stages of Catalyst Development
15.2 Development of a Catalytical Process: Hydrogenation of Benzene to Cyclohexane
15.3 Selection and Testing of Catalysts in Practice
Exercises
References

Chapter 16: Catalysis Reactors

16.1 Plug Flow Reactor (PFR)
16.2 Continuous Stirred-Tank Reactor (CSTR)
16.3 Reactor Calculations
16.4 Two-Phase Reactors
16.5 Three-Phase Reactors
16.6 Reactors for Homogeneously Catalyzed Reactions
16.7 New Reactor Concepts
Exercises
References

Chapter 17: Economic Importance of Catalysts

References

Chapter 18: Future Development of Catalysis

18.1 Homogeneous Catalysis
18.2 Heterogeneous Catalysis
References

Solutions to the Exercises

Chapter 1
Chapter 2
Chapter 3
Chapter 4
Chapter 5
Chapter 6
Chapter 7
Chapter 8
Chapter 9
Chapter 10
Chapter 11
Chapter 12
Chapter 13
Chapter 14
Chapter 15
Chapter 16

Index

End User License Agreement

List of Illustrations

Chapter 1: Introduction

Figure 1.1 Catalytic cycle.
Scheme 1.1 Parallel and sequential reactions.
Scheme 1.2 Reactions of synthesis gas.
Scheme 1.3 Classification of catalysts.

Chapter 2: Homogeneous Catalysis with Transition Metal Catalysts

Scheme 2.1 Tendency to undergo oxidative addition for the metals of groups 8–10.
Scheme 2.2 Course of a homogeneously catalyzed reaction according to the 16/18-electron rule.
Scheme 2.3 Cobalt-catalyzed hydroformylation of a terminal alkene in terms of the 16/18-electron rule.
Figure 2.1 Carbonylation of 1-decene in a high-pressure IR apparatus; catalyst [(PPh₃)₃CuCl]/tetramethylethylenediamine, solvent THF. Bands: (1) 2130 cm⁻¹, dissolved CO; (2) 2060 cm⁻¹, Cu(CO) complex; (3) 1710–1720 cm⁻¹, aldehyde; and (4) 1640 cm⁻¹, 1-decene.
Figure 2.2 Schematic of the high-pressure IR apparatus (University of Applied Sciences Mannheim). (1) Magnetic piston autoclave with recirculating pump; (2) heating strip; (3) microfilter; (4) high-pressure IR cuvette; and (5) magnetic coil.
Figure 2.3 Chemical shifts in ³¹P NMR spectra of transition metal chelate rings with bidentate phosphines ([2], used with permission of Wiley-VCH).
Figure 2.4 Pd-catalyzed methoxycarbonylation of ethene, hydride cycle [2].
Figure 2.5 ³¹P NMR investigation of the Pd-catalyzed methoxycarbonylation of ethene ([2], used with permission of Wiley-VCH).

Chapter 3: Homogeneously Catalyzed Industrial Processes

Scheme 3.1 Homogeneous transition metal-catalyzed reactions carried out industrially [1].
Scheme 3.2 Mechanism of the hydroformylation of propene with [HRh(CO)(PPh₃)₃].
Figure 3.1 Ruhrchemie/Rhône-Poulenc process for the hydroformylation of propene.
Scheme 3.3 Carbonylation of methanol to produce acetic acid (Monsanto process).
Scheme 3.4 Mechanism for the oxidation of ethylene to acetaldehyde in the Wacker process (chloride ligands omitted).
Figure 3.2 Acetaldehyde production in the two-stage Wacker–Hoechst process.
Scheme 3.5 Proposed mechanism for the oxidation of cyclohexane via free radicals.
Scheme 3.6 Proposed mechanism for the palladium-catalyzed Suzuki coupling.
Figure 3.3 Biphasic system of the SHOP process.
Scheme 3.7 Block schematic of the SHOP process.
Scheme 3.8 Schematic of ethylene oligomerization with nickel complex catalysts.
Scheme 3.9 Telomerization of butadiene.
Scheme 3.10 Telomerization of butadiene with methanol.
Scheme 3.11 Hydrocyanation of butadiene.
Figure 3.4 Selection of chiral phosphine ligands.
Figure 3.5 Mn-salen (Jacobsen complex).
Scheme 3.12 Simplified mechanism of alkene metathesis.
Figure 3.6 Tungsten carbene complex.
Figure 3.7 Carbene complexes as metathesis catalysts [6].
Figure 3.8 Fluorous phosphine ligand.
Scheme 3.13 Rhodium-catalyzed coupling of ethylene and butadiene.

Chapter 4: Biocatalysis

Figure 4.1 Biocatalysis as an interdisciplinary area.
Figure 4.2 Lock and key model for enzyme–substrate interaction.
Figure 4.3 Effect of coenzyme during acetaldehyde reduction.
Figure 4.4 Normalized rate for an enzyme-catalyzed reaction.
Figure 4.5 Lineweaver–Burk plot [6].
Figure 4.6 Lineweaver–Burk plot for the urea reaction.
Figure 4.7 Biosynthetic route to aspartame.
Figure 4.8 Pilot scale enzyme membrane reactor for the production of l-amino acids (Degussa AG).
Figure 4.9 6-aminopenicillanic acid (6-APA)
Figure 4.10 Manufacturing active pharmaceutical ingredients at Macfarlan Smith (Johnson Matthey).
Figure 4.11 Herbicide Outlook™.

Chapter 5: Heterogeneous Catalysis: Fundamentals

Figure 5.1 Individual steps of a heterogeneously catalyzed gas-phase reaction.
Figure 5.2 Concentration–position curves in the film diffusion region (a), the pore diffusion region (b), and the kinetic region (c).
Figure 5.3 Dependence of effective reaction rate on temperature.
Figure 5.4 Langmuir isotherm.
Figure 5.5 Langmuir–Hinshelwood mechanism (schematic).
Figure 5.6 Limiting cases of a bimolecular gas-phase reaction according to the Langmuir–Hinshelwood mechanism.
Figure 5.7 Eley–Rideal mechanism (schematic).
Figure 5.8 Bimolecular gas-phase reaction with the Eley–Rideal mechanism.
Figure 5.9 Course of a heterogeneously catalyzed gas-phase reaction $c05-math-0058$ . E_a,0 = activation energy of the homogeneous uncatalyzed gas-phase reaction; E_a,1 = true activation energy; E_a,2 = apparent activation energy of the catalyzed reaction; Z₁ = transition state of the gas-phase reaction; Z₂ = transition state of the surface reaction; and ΔH_R = reaction enthalpy.
Figure 5.10 Molecular chemisorption of ethylene on a Pt surface.
Figure 5.11 Potential energy and interatomic distances in the adsorption of hydrogen on nickel. Curve 1: physisorption (0.32 nm, $c05-math-0064$ ); curve 2: chemisorption (0.16 nm, $c05-math-0065$ ); E_D = dissociation energy of H₂ (218 kJ mol⁻¹); and E_A = activation energy for adsorption.
Figure 5.12 Dissociative adsorption of hydrogen on nickel surfaces.
Figure 5.13 Relative activity of metals for the decomposition of formic acid as a function of the heat of formation of the metal formates (volcano plot).
Scheme 5.1 Mechanism for the hydrogenation of an alkene [17].
Scheme 5.2 Mechanism for the hydrogenation of acetylene.
Figure 5.14 Lattice planes in a cubic lattice with Miller indices.
Figure 5.15 Neighboring atoms and free valences of nickel surfaces in the face-centered cubic (fcc) lattice.
Figure 5.16 Model of a single-crystal surface (BASF, Ludwigshafen, Germany).
Figure 5.17 Ethylene hydrogenation as a function of the metal–metal distance in the lattice [8].
Figure 5.18 Oxidation of CO on platinum surfaces.
Figure 5.19 Electron transfer between catalyst and substrate.
Figure 5.20 Acceptor and donor functions according to the band model: (a) no adsorption; (b) acceptor; and (c) donor E_F,0 = Fermi level; E_F = Fermi energy.
Figure 5.21 Adsorption of hydrogen on copper–nickel alloys.
Figure 5.22 Specific activity of copper–nickel alloys for the dehydrogenation of cyclohexane and the hydrogenolysis of ethane to methane at 316 °C.
Figure 5.23 Intrinsic semiconductor with excitation energy.
Figure 5.24 Semiconductors and how they function: (a) n-type semiconductor and (b) p-type semiconductor.
Scheme 5.3
Figure 5.25 Relative activities of metal oxides in the decomposition of N₂O [28].
Scheme 5.4 Hydrogenation of ethylene on ZnO.
Figure 5.26 Acid centers in Al₂O₃.
Figure 5.27 Mechanism of gas-phase dehydration of ethanol on aluminum oxide.
Figure 5.28 Important properties of an industrial catalyst.
Figure 5.29 Structure of supported catalysts (Fonds der Chemischen Industrie, Frankfurt am Main, Germany, Folienserie Katalyse Nr. 19).
Scheme 5.5 Reforming of n-hexane on a Pt/Al₂O₃ supported catalyst.
Scheme 5.6 Reforming of methane with CO₂ on supported Rh/Al₂O₃ catalysts [31].
Figure 5.30 The action of potassium promoters in the dissociative chemisorption of N₂ on iron catalysts.
Figure 5.31 Deactivation behavior of catalysts [6].
Figure 5.32 Mechanisms of catalyst deactivation (M = metal) [6].
Figure 5.33 Dehydrogenative coking.
Figure 5.34 Catalyst deactivation in reforming processes [8].
Figure 5.35 Catalyst regeneration and loss of activity during a process.
Scheme 5.7 Regeneration of naphtha reforming catalysts [36].
Figure 5.36 Instruments of catalyst investigation.
Figure 5.37 Pore size spectrum in a refinery catalysts (BASF SE Ludwigshafen, Germany) [38]. There could be three differentiated classes of pores with a very bright distribution: (a) a few fairly large cracks (∼100 µm), (b) fine channels between the grains (∼600 nm), and (c) very small pores (∼6 nm).
Figure 5.38 Typical isotherm for physisorption.
Figure 5.39 Sorptometer (Catalysis laboratory, Mannheim University of Applied Sciences, Germany).
Figure 5.40 Scheme of a TPD spectrum of ammonia desorbing from zeolite [41].
Figure 5.41 Principle of a device for temperature-programmed reduction (TPR) [4].
Figure 5.42 Agglomeration of platinum crystallites in a platinum/graphite catalyst: quantification of the process by XPS (top middle) and visualization by TEM (bottom) (BASF SE, Ludwigshafen, Germany).
Figure 5.43 Investigation of a catalyst surface in an ESCA apparatus (BASF SE, Ludwigshafen, Germany).
Figure 5.44 ESCA spectrum of an Ag/Al₂O₃ supported catalyst [42].
Figure 5.45 ISS spectra of a new and used ethylene oxide catalyst [22].

Chapter 6: Catalyst Shapes and Production of Heterogeneous Catalysts

Figure 6.1 Various shaped catalyst bodies (BASF, Ludwigshafen, Germany).
Scheme 6.1 Preparation methods for solid catalysts.
Scheme 6.2 Production of a precipitated catalyst [6].
Figure 6.2 Production of noble metal catalysts at the company Degussa, Hanau-Wolfgang, Germany.
Figure 6.3 Steps in the preparation of a porous powder via the sol–gel method ([8], used with permission of Wiley-VCH).
Scheme 6.3 Manufacturing of zeolites.
Scheme 6.4 Production of supported metal catalysts by impregnation.
Figure 6.4 Principle of catalyst preparation by incipient wetness impregnation.
Figure 6.5 Influence of the rate of drying on the profile of pores and particles.
Figure 6.6 Cross section of a shell catalyst (magnification 18×). Influence of the shell thickness on the selectivity of acrolein synthesis (BASF, Ludwigshafen, Germany): $c06-math-0009$
Figure 6.7 Different metal distributions in pellets of diameter 6 mm consisting of a metal on a support (Degussa, Hanau-Wolfgang, Germany). (a) Shell catalyst with normal shell thickness; (b) shell catalyst with an extremely thin shell; (c) shell catalyst with a thick shell; (d) impregnated catalyst; and (e) catalyst with ring distribution.
Figure 6.8 Modern catalyst production plant (BASF, Ludwigshafen, Germany).
Figure 6.9 Acidic ion-exchange resin.
Figure 6.10 Manufacturing extruded heavy duty diesel emission control catalysts in Redwitz, Germany (Johnson Matthey).

Chapter 7: Shape-Selective Catalysis: Zeolites

Figure 7.1 Truncated octahedra as structural units of zeolites. (a) Sodalite cage (β-cage) and (b) sodalite cage (schematic).
Figure 7.2 Framework structure of zeolite A with α-cage.
Figure 7.3 Y zeolite (faujasite).
Figure 7.4 Pentasil zeolite with channel structure.
Figure 7.5 Shape selectivity of zeolites with examples of reactions. (a) Reactant selectivity: cleavage of hydrocarbons. (b) Product selectivity: methylation of toluene. (c) Restricted transition state selectivity: disproportionation of m-xylene.
Figure 7.6 Calcination of an HY zeolite: equilibrium between Brønsted and Lewis acid centers [13].
Scheme 7.1 Bifunctionality of metal-doped zeolites: isomerization and hydrogenation.
Figure 7.7 Modification possibilities of zeolite catalysts.

Chapter 8: Heterogeneously Catalyzed Processes in Industry

Figure 8.1 Supported metal catalyst with large reaction surface (Doduco).
Figure 8.2 Catalytic afterburning of the off-gases from a cyclohexanone plant (BASF, Antwerp).
Scheme 8.1 Simplified mechanism of ammonia synthesis.
Scheme 8.2 Synthesis of ammonia from natural gas.
Scheme 8.3 Reaction steps in the hydrogenation of fats.
Scheme 8.4 Mechanism of methanol synthesis.
Figure 8.3 Methanol plant (BASF, Ludwigshafen, Germany).
Scheme 8.5 Oxidation of propene on various metal oxide catalysts.
Scheme 8.6 Oxidation of propene to acrolein on Bi/Mo catalysts [12].
Scheme 8.7 Postulated reaction mechanism for the ammoxidation of propene [10].
Figure 8.4 SOHIO process for the ammoxidation of propene.
Figure 8.5 HPPO process (BASF SE) [14].
Figure 8.6 Oxidation of butane to maleic anhydride in a fixed-bed reactor.
Figure 8.7 Areas of fine chemicals.
Scheme 8.8 Atom efficiency in acetophenone production [16].
Scheme 8.9 Influence of yield improvement in a multistep process.
Figure 8.8 Use of metal catalysis in fine chemical synthesis.
Figure 8.9 Operation of a continuous high-pressure hydrogenation plant (CATATEST plant, VINCI technologies, France; high-pressure laboratory, Mannheim University of Applied Sciences, Germany).
Figure 8.10 A hydrogenation catalyst is introduced into a pilot plant in order to test it under process-relevant conditions (BASF SE, Ludwigshafen, Germany).
Figure 8.11 Comparison of stoichiometric and catalytic routes in oxidation processes.

Chapter 9: Refinery Processes and Petrochemistry

Scheme 9.1 Catalytic processes in a petroleum refinery.
Figure 9.1 Scheme of a modern FCC process.
Figure 9.2 Cracker in Secunda (Sasol Ltd., South Africa).
Figure 9.3 Model of a typical hydrocracking catalysts system.
Scheme 9.2 Major reactions during catalytic reforming.
Figure 9.4 Reforming catalyst.
Figure 9.5 Scheme of a reforming process.
Scheme 9.3 Major reactions during steam reforming.
Figure 9.6 Catalytic steam reforming unit [13].
Scheme 9.4 Conversion of natural gas to fuels and chemical raw materials [13].
Scheme 9.5 Major reactions in Fischer–Tropsch synthesis.
Figure 9.7 Production of MTBE by catalytic distillation.

Chapter 10: Electrocatalytic Processes

Figure 10.1 Electrochemical asymmetric bishydroxylation using a double mediator system in the presence of chiral ligands.
Figure 10.2 Complete fuel cell system including gas processing.
Figure 10.3 Scheme of a PEM fuel cell.
Figure 10.4 Fuel cell device for education (Leybold Didactic; University of Applied Sciences Mannheim, Germany, Institute of Chemical Process Engineering).
Figure 10.5 Different reaction pathways for electrochemical oxygen reduction in acidic electrolytes [10].
Figure 10.6 Scheme of methanol oxidation on Pt catalysts [7].

Chapter 11: Environmental Catalysis and Green Chemistry

Figure 11.1 Conversion profile in a three-way-catalyst.
Figure 11.2 Automobile exhaust catalyst (Fonds der Chemischen Industrie, Frankfurt am Main, Germany, Folienserie Nr. 19, Katalyse).
Figure 11.3 Honeycomb catalysts for air purification (Süd-Chemie AG, Heufeld, Germany).
Figure 11.4 Conversion-temperature profiles for different SCR catalysts (BASF SE, Ludwigshafen, Germany) [9].
Figure 11.5 Action of a NO_x-storage reduction catalyst.
Figure 11.6 Typical afterburning process of a hydrocarbon.
Figure 11.7 Scheme of a catalytic afterburning plant.
Figure 11.8 Structures of some ionic liquids.
Figure 11.9 Substitution of common solvents.

Chapter 12: Phase-Transfer Catalysis

Figure 12.1 Structures of phase-transfer catalysts.
Figure 12.2 The extraction mechanism of phase-transfer catalysis [4].

Chapter 13: Catalytic Processes with Renewable Materials

Scheme 13.1 Conversion of biomass to fuels and chemicals [4].
Figure 13.1 Distribution of renewable raw materials (total 180 billion t/a) across material groups [12].
Figure 13.2 Palm oil plantation in Costa Rica.
Scheme 13.2 Fuels by gasification of biomass.
Scheme 13.3 Lignocellulose feedstock biorefinery.
Scheme 13.4 Value-chains for the production of chemicals and end-products from biomass.
Scheme 13.5 Glucose as one of the platform chemicals from cellulose.
Scheme 13.6 5-HMF as a platform for chemicals.
Figure 13.3 Monoterpenes.

Chapter 14: Polymerization Catalysis

Figure 14.1 Isotactic and syndiotactic polypropylene.
Scheme 14.1 Polymerization of ethylene at a metal center (M).
Figure 14.2 Catalytic active metallocene complex.
Figure 14.3 DSM catalyst “Lovacat.”
Scheme 14.2 Comparison of polyethylene types.
Figure 14.4 Gas-phase process for HDPE.
Scheme 14.3 Ziegler polymerization of ethylene with Ti/Al catalysts.

Chapter 15: Planning, Development, and Testing of Catalysts

Figure 15.1 Main steps in catalyst development.
Scheme 15.1 Target quantities and influences on the choice of catalyst [3].
Figure 15.2 Hydrogenation of benzene to cyclohexane (IFP process) [1].
Scheme 15.2 Procedures for choosing a catalyst.
Figure 15.3 Scheme of a differential reactor.
Figure 15.4 Catalyst test reactors.
Figure 15.5 Jet-loop reactor for catalyst investigations (high-pressure laboratory, Mannheim University of Applied Sciences, Germany). (1) Thermal mass flow controller (up to 200 bar); (2) nozzle, interchangeable; (3) catalyst pellets on wire mesh; (4) central tube; (5) heating band 500 W; (6) microfilter; (7) precision feed valve; (8) supplementary heating; and (9) gas meter.
Figure 15.6 Jet loop reactor (high-pressure laboratory, Mannheim University of Applied Sciences, Germany).
Figure 15.7 Gas chromatogram of methanol synthesis in the jet-loop reactor. Reaction conditions: $c15-math-0022$ , 40 bar, 25 g catalyst, $c15-math-0023$ , nozzle diameter 0.1 mm.
Figure 15.8 Industrial catalyst test center (Süd-Chemie AG, Heufeld, Germany).
Figure 15.9 Evaluation of the data from an integral reactor.
Figure 15.10 Polynomial fit of X_A versus TF (example integral reactor).
Figure 15.11 Kinetic study of the hydrogenation of benzaldehyde in a stirred autoclave operating in suspension mode [15].
Figure 15.12 Hydrogenation of benzaldehyde in a stirred autoclave: dependence of reaction rate on H₂ pressure [15].
Figure 15.13 Residence time spectra in a trickle-bed reactor as a function of liquid flow (LF) [18]. Reactor length 1 m, diameter, 25.4 mm, Cu/Zn mixed-oxide catalyst (tablets 6 × 3 mm), liquid phase tert-butanol, gas flow 10 l min⁻¹, 100 bar H₂ pressure, 25 °C.
Figure 15.14 ISIM program for the simulation of a trickle-bed reactor for the high-pressure hydrogenation of a lactone [18].
Figure 15.15 Lactone hydrogenation in a trickle-bed reactor: conversion profiles as a function of liquid flow at constant liquid holdup [18].
Figure 15.16 Lactone hydrogenation in a trickle-bed reactor: conversion profiles taking into account the external liquid holdup [18].
Figure 15.17 Lactone hydrogenation in a trickle-bed reactor: conversion profiles as a function of liquid flow and reactor length [18].
Figure 15.18 Lactone hydrogenation in a trickle-bed reactor: conversion profiles as a function of the global mass-transfer coefficient of hydrogen [18].
Figure 15.19 Lactone hydrogenation in a trickle-bed reactor: reaction rate profiles as a function of mass transfer [18].
Figure 15.20 384-fold single-bead reactor employed at hte AG, Heidelberg, Germany.
Figure 15.21 Stage-II parallel high-pressure reactor system (hte AG, Heidelberg, Germany).

Chapter 16: Catalysis Reactors

Figure 16.1 Influences on the design of catalysis reactors.
Figure 16.2 Comparison of a continuous stirred tank reactor (CSTR) with a plug flow reactor (PFR).
Figure 16.3 Conversion down the packed bed.
Figure 16.4 Partial pressure ratio profiles.
Figure 16.5 Examples of important gas–solid reactors [2].
Figure 16.6 Miniplant unit for the development of catalytical processes in three-phase reactions (Evonik AG, Marl, Germany).
Figure 16.7 Three-phase reactors.
Figure 16.8 Pilot plant with 0.2 l trickle-bed reactor (Hoffmann-La Roche, Kaiseraugst, Switzerland).
Figure 16.9 Variants of the suspension reactor.
Figure 16.10 0.5 l stirred autoclave reactor in a high-pressure box (Mannheim University of Applied Sciences, Germany).
Figure 16.11 Principle of a membrane reactor.
Figure 16.12 Opened microreactor module used in the exothermic synthesis of an ionic liquid in 100 kg/d scale. Fraunhofer ICT-IMM, Mainz, Germany.

Chapter 17: Economic Importance of Catalysts

Figure 17.1 Worldwide catalyst market according to application [5].

Chapter 18: Future Development of Catalysis

Figure 18.1 CH activation of alkanes [3] L_nM = catalyst (M = metal, L = ligand).
Figure 18.2 Development cycle of a product or process.
Figure 18.3 New catalysts – a key innovation in the future.

List of Tables

Chapter 1: Introduction

Table 1.1 History of the catalysis of industrial processes [3, 4]
Table 1.2
Table 1.3 Mole balance for methanol synthesis
Table 1.4 Comparison of homogeneous and heterogeneous catalysts
Table 1.5 Comparison of the key reactions of homogeneous and heterogeneous transition metal catalysis [12].

Chapter 2: Homogeneous Catalysis with Transition Metal Catalysts

Table 2.1 Typical cone angles for trivalent phosphorus ligands [9]
Table 2.2 Oxidative addition reactions on transition metal complexes; classification of the adding compounds

Chapter 3: Homogeneously Catalyzed Industrial Processes

Table 3.1 Industrial processes with homogeneous transition metal catalysis.
Table 3.2 Production of selected chemicals by homogeneous catalysis.
Table 3.3 Industrial propene hydroformylation processes [9]

Chapter 4: Biocatalysis

Table 4.1 Advantages and disadvantages of biocatalysts and enzymes [1]
Table 4.2 The six categories of enzymes according to the type of reaction [3]
Table 4.3 Acrylamide by chemical process and by biotransformation

Chapter 5: Heterogeneous Catalysis: Fundamentals

Table 5.1 Comparison of homogeneous and heterogeneous catalytic reactions
Table 5.2 Comparison of physisorption and chemisorption
Table 5.3 Examples of chemisorption processes
Table 5.4 IR bands of surface CO complexes on supported Ni catalysts
Table 5.5 IR bands of ethylene complexes
Table 5.6 Relative reaction rates on transition metal catalysts
Table 5.7 Structure and lattice spacings (distance to next-nearest neighbor in nm) of metals [20]
Table 5.8 Classification of metal-catalyzed reactions [1].
Table 5.9 Steric effects in chemical reactions.
Table 5.10 Adsorption and hydrogenation of ethylene on nickel surfaces [18]
Table 5.11 Classification of solid-state catalysts
Table 5.12 Relative catalytic activity of metals [9, 19, 20]
Table 5.13 Bimetallic catalysts in industrial processes.
Table 5.14 Hydrogenation of ethyl acetate to ethanol with Rh/Sn-SiO₂ catalysts [25].
Table 5.15 Hydrogenation of crotonaldehyde with bimetallic catalysts [26]
Table 5.16 Modification of the catalytic properties of the platinum group metals by addition of other metals [18]
Table 5.17 Excitation energies of semiconductors
Table 5.18 Behavior of nonstoichiometric semiconductor oxides
Table 5.19 Classification of the metal oxides according to their electronic properties.
Table 5.20 Oxidation of CO with metal oxide catalysts
Table 5.21 Decomposition of ethanol on semiconductor oxides
Table 5.22 Classification of acid/base catalysts [19]
Table 5.23 Performance of aluminum oxides in the dehydration of ethanol [29]
Table 5.24 Acidic catalysts for various reactions arranged in the order of increasing acidity [9]
Table 5.25 Important catalyst supports and their applications
Table 5.26 Selection of catalyst supports [20].
Table 5.27 Hydrogenolysis of ethane on supported nickel catalysts (10% Ni) [8]
Table 5.28 Dehydrogenation of cyclohexane to benzene on supported platinum catalysts at 773 K [30]
Table 5.29 Influence of support materials on the hydrogenation of CO with rhodium catalysts
Table 5.30 Examples of promoters in the chemical industry [19]
Table 5.31 Causes of deactivation in large-scale industrial processes
Table 5.32 Catalyst poisons and inhibitors in chemical processes [19]
Table 5.33 Recycling of precious metal catalysts [38]
Table 5.34 Specific surface areas of catalysts and support materials
Table 5.35 Specific chemisorption for the characterization of metal surfaces.
Table 5.36 Comparison of surface physics and industrial heterogeneous catalysis.

Chapter 6: Catalyst Shapes and Production of Heterogeneous Catalysts

Table 6.1 Shaping of catalysts
Table 6.2 Comparison of homogeneous and heterogenized catalysts in industrial reactions

Chapter 7: Shape-Selective Catalysis: Zeolites

Table 7.1 Characteristics of important zeolites.
Table 7.2 Molecular diameters and pore sizes of zeolites [1, 8]
Table 7.3 Constraint index (CI) for some typical catalysts at 316 °C [9]
Table 7.4 Relative rate of cleavage of heptanes on H-ZSM-5 at 325 °C [10]
Table 7.5 Product distribution in the ethylation of toluene [8]
Table 7.6 Effect of the metal ion in faujasite on the dealkylation of cumene [10]
Table 7.7 Classification of acidic zeolites according to increasing Si/Al ratio [6]
Table 7.8 Shape-selective hydrogenation [8]
Table 7.9 Important catalytic processes involving zeolites.
Table 7.10 Organic syntheses with zeolite catalysts [9, 7].

Chapter 8: Heterogeneously Catalyzed Processes in Industry

Table 8.1 Heterogeneous catalysis for the production of industrial gases and inorganic chemicals [3]
Table 8.2 Heterogeneously catalyzed processes for the production of organic chemicals [3]
Table 8.3 Heterogeneously catalyzed processes in refinery technology [3]
Table 8.4 Heterogeneous catalysts in environmental protection
Table 8.5 Fine versus bulk chemicals [16]
Table 8.6 Comparison of stoichiometric and catalytic reactions in fine chemicals synthesis [8]
Table 8.7 p-Methoxyacetophenone via zeolite-catalyzed versus classical Friedel–Crafts acylation [16]

Chapter 9: Refinery Processes and Petrochemistry

Table 9.1 Process conditions and performance characteristics for hydrotreating of light and heavy feeds
Table 9.2 Propylene by FCC-based processes [7]
Table 9.3 Comparison of catalysts for C5–C6 hydroisomerization reactions
Table 9.4 Fixed-bed and fluidized-bed technologies in Fischer–Tropsch synthesis (wt%)

Chapter 10: Electrocatalytic Processes

Table 10.1 Types of fuel cell
Table 10.2 Electrocatalysts for the main fuel cell systems [9, 10]

Chapter 11: Environmental Catalysis and Green Chemistry

Table 11.1 Comparison of process temperatures for the oxidation of VOCs in afterburning processes
Table 11.2 Results of the aldol condensation with various catalysts [14]

Chapter 13: Catalytic Processes with Renewable Materials

Table 13.1 Derivatization reactions of fats and oils

Chapter 15: Planning, Development, and Testing of Catalysts

Table 15.1 Development of a catalyst for the oxidation of propene to acrolein [4]
Table 15.2 Catalyst screening.
Table 15.3 Hydrogenation of substituted 2-cyanonitro compounds [7].
Table 15.4 Catalyst screening in the hydrogenation of substituted 2-nitrobenzonitrile.
Table 15.5 Solvent screening in the hydrogenation of substituted 2-nitrobenzonitrile.
Table 15.6
Table 15.7 Hydrogenation of benzaldehyde in a trickle-bed reactor: measured values and model calculations [15]
Table 15.8 Measured and calculated conversion in the trickle-bed reactor; influence of the external holdup
Table 15.9 Stages I and II technologies for high-throughput experimentation [19]

Chapter 16: Catalysis Reactors

Table 16.1 Comparison of trickle-bed and suspension reactors
Table 16.2 Various technologies for the hydrogenation of adiponitrile [4]

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Preface to the Third Edition

Since the second edition of this book the field of industrial catalysis has made significant progress. New techniques in catalyst development have become relevant and many new processes were introduced in industry. The focus of this textbook is still to cover the fundamentals of homogeneous, heterogeneous catalysis, and biocatalysis, and to describe the industrial practice of catalysis and some special topics of applied catalysis.

The third edition has been extensively revised and updated. From the wealth of catalytical processes, a selection had to be made. Knowledge of some key processes is essential for the understanding of catalysis.

Entirely new are the chapters and sections.

refinery processes and petrochemistry;
catalytic processes with renewable materials;
polymerization catalysis;
catalyst shapes and production of heterogeneous catalysts;
recycling of homogeneous catalysts;
regeneration and recycling of heterogeneous catalysts;
new reactor concepts.

In some other sections, additional examples of catalytical processes are addressed, for instance, alkene metathesis, telomerization of butadiene, adipodinitrile, maleic anhydride and phthalic anhydride, propylene oxide, pharmaceuticals, and fine chemicals. Many new exercises including solutions were added, they should help users develop a better understanding of the material.

The book is largely the result of courses for chemical engineers I have given at the Mannheim University of Applied Sciences, some universities abroad, and several vocational training seminars for chemists and engineers in industry. I hope that this edition will still be useful to students and to engineers, chemists, and professionals who work in the chemical industry and related industries. The book is particularly well suited for the self-study of people who have a basic knowledge of chemistry and chemical reaction engineering.

My great appreciation is given to the following companies and institutions, which provided new pictures for this edition: BASF SE, Ludwigshafen; Johnson Matthey Plc, London, UK; Sasol Ltd., South Africa; Fonds der Chemischen Industrie, Frankfurt am Main; Chemieanlagenbau Chemnitz GmbH, Evonik Services GmbH, Hanau-Wolfgang; Fraunhofer ICT-IMM, Mainz.

I would like to thank the production team at Wiley-VCH, particularly Dr. Elke Maase and the editors Dr. Claudia Ley and Stefanie Volk for their kind assistance and support.

Furthermore, I am grateful for the many helpful comments by the coworkers of SPi Global during typesetting. Finally, I thank my wife Julia again for her pacience and understanding during realization of this project.

I hope that the reader will see that catalysis is one of the most exciting areas in chemistry.

Jens Hagen

Östringen

April 2015

Abbreviations

A	area (m²)
A*	adsorbed (activated) molecules of component A
a	catalyst activity
a_s	area per mass (m² kg⁻¹)
A	electron acceptor
Ac	acetyl CH₃CO-
AAS	atomic absorption spectroscopy
ADH	alcohol dehydrogenase enzyme
ADMET	acyclic diene metathesis
6-APA	6-aminopenicillanic acid
ads	adsorbed (subscript)
AES	Auger electron spectroscopy
aq	aqueous solution (subscript)
bcc	body-centered cubic
bipy	2,2′-bipyridine
Bu	butyl C₄H₉-
BET	Brunauer, Emmet, and Teller (adsorption process)
c_i	concentration of component i (mol l⁻¹)
CB	conduction band
C.I.	constraint index
CMR	catalytical membrane reactor
Cp	cyclopentadienyl C₅H₅-
CSTR	continuous stirred tank reactor
D	diffusion coefficient (m² s⁻¹)
d	deactivation (subscript)
D	electron donor
DMFC	direct methanol fuel cell
DMSO	dimethyl sulfoxide
DVB	divinylbenzene
E	E factor, rate of waste (kg) per product unit (kg)
E_a	activation energy (J mol⁻¹)
E_F,0	Fermi level
E	enzyme
ee	enantiomeric excess (%)
eff	effective (subscript)
E_i	ionization energy
E_r	redox potential (V)
Et	ethyl C₂H₅-
ESCA	electron spectroscopy for chemical analysis
ESR	electron spin resonance spectroscopy
ETBE	ethyl tert-butyl ether
e	electrons
F	Faraday constant (96 485 C mol⁻¹)
fcc	face-centered cubic
FCC	fluid catalytic cracking
ΔG	Gibb's free energy (J mol⁻¹)
G	gas (subscript, too)
GDP	gross domestic product
GHSV	gas hourly space velocity (h⁻¹)
GTL	gas to liquids
H	Henry's law constant
H_ex	external holdup
ΔH_ads	adsorption enthalpy (J mol⁻¹)
ΔH_f	enthalpy change of formation (J mol⁻¹)
H_m	modified Henry's law constant
ΔH_R	reaction enthalpy (J mol⁻¹)
HC	hydrocarbon
HDN	hydrodenitrogenation
HDPE	high-density polyethylene
HDS	hydrodesulfurization
5-HMF	5-hydroxymethylfurfural
HPA	heteropolyacids
HPPO	hydrogen peroxide to propylene oxide
hcp	hexagonal close packing
i	intrinsic
I	inhibitor
ICP	inductively coupled plasma
IL	ionic liquid
ISS	ion-scattering spectroscopy
K	equilibrium constant
K_i	adsorption equilibrium constant of component i
K_i	inhibition constant
K_M	Michaelis constant
k	reaction rate constant
k₀	pre-exponential factor
k_L a_L	gas–liquid mass transfer coefficient
k_S a_S	liquid–solid mass transfer coefficient
k_tot	global mass transfer coefficient
L	liquid (subscript)
L	ligand
LCF	lignocellulose feedstock
LDPE	low-density polyethylene
l-DOPA	2-amino-3-(3,4-dihydroxyphenyl)propionic acid
LEED	low-energy electron diffraction
LHSV	liquid hourly space velocity (h⁻¹)
LLDPE	linear low-density polyethylene
LPG	liquefied petrol gas
LSR	light straight run (naphtha)
LF	liquid feed (l min⁻¹)
M	metal
m	mass (kg)
m_cat.	mass of catalyst (kg)
MA	maleic anhydride
MAO	methylaluminoxane
MCM-41	mesoporous material
MSR	microstructured reactor
MTG	methanol to gasoline
MTO	methanol to olefins
MTBE	methyl tert-butyl ether
MTP	methanol to propylene
MWD	molecular weight distribution
Me	methyl CH₃-
n	number of moles (mol)
n	order of reaction
n	degree of polymerization
$flast-math-0001$	flow rate (mol s⁻¹)
$flast-math-0002$	feed flow rate of starting material A (mol s⁻¹)
NAD	nicotinamide adenine dinucleotide cofactor
NSR	NO_x storage reduction
OCS	oxygen storage component
ODE	ordinary differential equation
ON	octane number
Oxad	oxidative addition
P	total pressure (bar)
PA	phthalic anhydride
PE	polyethylene
PEG	polyethylene glycol
PEMFC	proton exchange membrane fuel cell
PFR	plug flow reactor
PP	polypropylene
PVI	pore volume impregnation
Ph	phenyl C₆H₅-
PPh₃	triphenylphosphine
PTC	phase-transfer catalysis
p	pressure (bar)
p_i	partial pressure of component i (bar)
py	pyridine
R	ideal gas law constant (J mol⁻¹ K⁻¹)
R	recycle ratio
R	alkyl
RCM	ring-closing metathesis
ROMP	ring-opening metathesis polymerization
RON	research octane number
RTD	residence time distribution
r	reaction rate (mol l⁻¹ h⁻¹)
r_eff	effective reaction rate per unit mass of catalyst (mol kg⁻¹ h⁻¹)
rel	relative (subscript)
r_d	deactivation rate
S	surface area (m² kg⁻¹)
ΔS	entropy change (J mol⁻¹ K⁻¹)
S_p	selectivity (mol mol⁻¹) or (%)
S	solid (subscript, too)
SCR	selective catalytic reduction
SIMS	secondary-ion mass spectroscopy
SLPC	supported liquid-phase catalysts
SMSI	strong metal-support interaction
SSPC	supported solid-phase catalysts
STEM	scanning transmission electron microscopy
S⁻¹	mass index, ratio of all the materials (kg) to the product (kg)
S	substrate
sc	supercritical
STY	space time yield (mol l⁻¹ h⁻¹, kg l⁻¹ h⁻¹)
T	temperature (K)
TAME	tert-amyl methyl ether
TBGE	tert-butylglycerol ether
TEM	transmission electron microscopy
TF	time factor $flast-math-0003$
TOF	turnover frequency (s⁻¹)
TON	turnover number (mol mol⁻¹ s⁻¹)
t	time (s, h)
TPD	temperature-programmed desorption
TPPMS	triphenylphosphine monosulfonate
TPPTS	triphenylphosphine trisulfonate
TPR	temperature-programmed reduction
TS 1	titanium(IV) silicalite zeolite catalyst
TWC	three-way catalyst
U	cell voltage (V)
V	volume (m³)
$flast-math-0004$	volumetric flow rate
V_R	reaction volume (m³)
VB	valence band
VGO	vacuum gas oil
VOC	volatile organic compound
VPO	vanadium–phosphorous oxide
WGS	water gas shift (reaction)
WHSV	weight hourly space velocity (kg kg_cat⁻¹ h⁻¹ or h⁻¹)
X	conversion (mol mol⁻¹) or (%)
XPS	X-ray photoelectron spectroscopy
XRD	X-ray diffraction
z	tube length (m)
$flast-math-0005$	void fraction of particle
λ	air/fuel intake ratio for gasoline engines
η	catalyst effectiveness factor
η	overpotential (V)
θ_i	degree of coverage of the surface of component i
v	stretching frequencies (IR) (cm⁻¹)
v_i	stoichiometric coefficient
ρ	density (g ml⁻¹)
ρ_cat.	pellet density of the catalyst (g ml⁻¹)
τ	tortuosity
σ	interfacial tension
φ₀	work function (eV)
*	active centers on the catalyst surface

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Abbreviations