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- Herausgeber: Wiley-VCH
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
Now in it's 3rd Edition, Industrial Catalysis offers all relevant information on catalytic processes in industry, including many recent examples. Perfectly suited for self-study, it is the ideal companion for scientists who want to get into the field or refresh existing knowledge.
The updated edition covers the full range of industrial aspects, from catalyst development and testing to process examples and catalyst recycling. The book is characterized by its practical relevance, expressed by a selection of over 40 examples of catalytic processes in industry. In addition, new chapters on catalytic processes with renewable materials and polymerization catalysis have been included. Existing chapters have been carefully revised and supported by new subchapters, for example, on metathesis reactions, refinery processes, petrochemistry and new reactor concepts.
"I found the book accesible, readable and interesting - both as a refresher and as an introduction to new topics - and a convenient first reference on current industrial catalytic practise and processes."
Excerpt from a book review for the second edition by P. C. H. Mitchell, Applied Organometallic Chemistry (2007)
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Seitenzahl: 756
Veröffentlichungsjahr: 2015
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Table of Contents
Cover
Related Titles
Title Page
Copyright
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
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Guide
Cover
Table of Contents
Preface
Begin Reading
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 [(PPh
3
)
3
CuCl]/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
31
P 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
31
P 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)(PPh
3
)
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 .
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; Z
1
= transition state of the gas-phase reaction; Z
2
= transition state of the surface reaction; and Δ
H
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, ); curve 2: chemisorption (0.16 nm, );
E
D
= dissociation energy of H
2
(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 N
2
O [28].
Scheme 5.4 Hydrogenation of ethylene on ZnO.
Figure 5.26 Acid centers in Al
2
O
3
.
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/Al
2
O
3
supported catalyst.
Scheme 5.6 Reforming of methane with CO
2
on supported Rh/Al
2
O
3
catalysts [31].
Figure 5.30 The action of potassium promoters in the dissociative chemisorption of N
2
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/Al
2
O
3
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):
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: , 40 bar, 25 g catalyst, , 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 H
2
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 H
2
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
n
M = 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-SiO
2
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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Jens Hagen
Industrial Catalysis
A Practical Approach
Third Completely Revised and Enlarged Edition
The Author
Prof. Dr. Jens Hagen
Johannes-Brahms-Str. 2
76684 Östringen
Germany
All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
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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 (m
2
)
A
*
adsorbed (activated) molecules of component
A
a
catalyst activity
a
s
area per mass (m
2
kg
−1
)
A
electron acceptor
Ac
acetyl CH
3
CO-
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 C
4
H
9
-
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 C
5
H
5
-
CSTR
continuous stirred tank reactor
D
diffusion coefficient (m
2
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 C
2
H
5
-
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
Δ
G
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
Δ
H
ads
adsorption enthalpy (J mol
−1
)
Δ
H
f
enthalpy change of formation (J mol
−1
)
H
m
modified Henry's law constant
Δ
H
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
k
0
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 CH
3
-
n
number of moles (mol)
n
order of reaction
n
degree of polymerization
flow rate (mol s
−1
)
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 C
6
H
5
-
PPh
3
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 (m
2
kg
−1
)
Δ
S
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
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 (m
3
)
volumetric flow rate
V
R
reaction volume (m
3
)
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)
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
φ
0
work function (eV)
*
active centers on the catalyst surface
Chapter 1Introduction
1.1 The Phenomenon Catalysis
Catalysis is the key to chemical transformations. Most industrial syntheses and nearly all biological reactions require catalysts. Furthermore, catalysis is the most important technology in environmental protection, that is, the prevention of emissions. A well-known example is the catalytic converter for automobiles.
Catalytic reactions were already used in antiquity, although the underlying principle of catalysis was not recognized at the time. For example, the fermentation of sugar to ethanol and the conversion of ethanol to acetic acid are catalyzed by enzymes (biocatalysts). However, the systematic scientific development of catalysis only began about 200 years ago, and its importance has grown up to the present day [1].
The term “catalysis” was introduced as early as 1836 by Berzelius in order to explain various decomposition and transformation reactions. He assumed that catalysts possess special powers that can influence the affinity of chemical substances.
A definition that is still valid today is due to Ostwald (1895): “a catalyst accelerates a chemical reaction without affecting the position of the equilibrium.” Ostwald recognized catalysis as a ubiquitous phenomenon that was to be explained in terms of the laws of physical chemistry.
While it was formerly assumed that the catalyst remained unchanged in the course of the reaction, it is now known that the catalyst is involved in chemical bonding with the reactants during the catalytic process. Thus, catalysis is a cyclic process: the reactants are bound to one form of the catalyst, and the products are released from another, regenerating the initial state.
In simple terms, the catalytic cycle can be described as shown in Figure 1.1. The intermediate catalyst complexes are in most cases highly reactive and difficult to detect.
Figure 1.1 Catalytic cycle.
In theory, an ideal catalyst would not be consumed, but this is not the case in practice. Owing to competing reactions, the catalyst undergoes chemical changes, and its activity becomes lower (catalyst deactivation). Thus, catalysts must be regenerated or eventually replaced.
Apart from accelerating reactions, catalysts have another important property: they can influence the selectivity of chemical reactions. This means that completely different products can be obtained from a given starting material by using different catalyst systems. Industrially, this targeted reaction control is often even more important than the catalytic activity.
Catalysts can be gases, liquids, or solids. Most industrial catalysts are liquids or solids, whereby the latter react only via their surface. The importance of catalysis in the chemical industry is shown by the fact that 75% of all chemicals are produced with the aid of catalysts; in newly developed processes, the figure is over 90%. Numerous organic intermediate products required for the production of plastics, synthetic fibers, pharmaceuticals, dyes, crop protection agents, resins, and pigments can only be produced by catalytic processes [2].
Most of the processes involved in crude oil processing and petrochemistry, such as purification stages, refining, and chemical transformations, require catalysts. Environmental protection measures such as automobile exhaust control and purification of off-gases from power stations and industrial plant would be inconceivable without catalysts.
Catalysts have been successfully used in the chemical industry for more than 100 years, examples being the synthesis of sulfuric acid, the conversion of ammonia to nitric acid, and catalytic hydrogenation. Later developments include new highly selective multicomponent oxide and metallic catalysts, zeolites, and the introduction of homogeneous transition metal complexes in the chemical industry. This was supplemented by new high-performance techniques for probing catalysts and elucidating the mechanisms of heterogeneous and homogenous catalysis.
The brief historical survey given in Table 1.1 shows just how closely the development of catalysis is linked to the history of industrial chemistry [4].
Table 1.1 History of the catalysis of industrial processes [3, 4]
Catalytic reaction
Catalyst
Discoverer or company/year
Sulfuric acid (lead chamber process)
NO
x
Désormes, Clement, 1806
Chlorine production by HCl oxidation
CuSO
4
Deacon, 1867
Sulfuric acid (contact process)
Pt, V
2
O
5
Winkler, 1875; Knietsch, 1888 (BASF)
Nitric acid by NH
3
oxidation
Pt/Rh nets
Ostwald, 1906
Fat hardening
Ni
Normann, 1907
Ammonia synthesis from N
2
, H
2
Fe
Mittasch, Haber, Bosch, 1908; Production, 1913 (BASF)
Hydrogenation of coal to hydrocarbons
Fe, Mo, Sn
Bergius, 1913; Pier, 1927
Oxidation of benzene, naphthalene to maleic anhydride or phthalic anhydride
V
2
O
5
Weiss, Downs, 1920
Methanol synthesis from CO/H
2
ZnO/Cr
2
O
3
Mittasch, 1923
Hydrocarbons from CO/H
2
(motor fuels)
Fe, Co, Ni
Fischer, Tropsch, 1925
Oxidation of ethylene to ethylene oxide
Ag
Lefort, 1930
Alkylation of olefins with isobutane to gasoline
AlCl
3
Ipatieff, Pines, 1932
Cracking of hydrocarbons
Al
2
O
3
/SiO
2
Houdry, 1937
Hydroformylation of ethylene to propanal
Co
Roelen, 1938 (Ruhrchemie)
Cracking in a fluidized bed
Aluminosilicates
Lewis, Gilliland, 1939 (Standard Oil)
Ethylene polymerization, low pressure
Ti compounds
Ziegler, Natta, 1954
Oxidation of ethylene to acetaldehyde
Pd/Cu chlorides
Hafner, Smidt (Wacker)
Ammoxidation of propene to acrylonitrile
Bi/Mo
Idol, 1959 (SOHIO process)
Olefin metathesis
Re, W, Mo
Banks, Bailey, 1964
Hydrogenation, isomerization, hydroformylation
Rh and Ru complexes
Wilkinson, 1964
Asymmetric hydrogenation
Rh/chiral phosphine
Knowles, 1974; L-Dopa (Monsanto)
Three-way catalyst
Pt, Rh/monolith
General Motors, Ford, 1974
Methanol conversion to hydrocarbons
Zeolites
Mobil Chemical Co., 1975
α-Olefins from ethylene
Ni/chelate phosphine
Shell (SHOP process) 1977
Sharpless oxidation, epoxidation
Ti/ROOH/tartrate
May & Baker, Upjohn, ARCO, 1981
Selective oxidations with H
2
O
2
Titanium zeolite (TS-1)
Enichem, 1983
Hydroformylation
Rh/phosphine/aqueous
Rhône-Poulenc/Ruhrchemie, 1984
Polymerization of olefins
zirconocene/MAO
Sinn, Kaminsky, 1985
Selective catalytic reduction SCR (power plants)
V, W, Ti oxides/monolith
∼1986
Acetic acid
Ir/I
−
/Ru
“Cativa”-process, BP Chemicals, 1996
W.S. Knowles, R. Noyori, K.B. Sharpless
Ti compounds, diphosphine ligands
Nobel Prize for asymmetric catalysis, 2001
Y. Chauvin, R.S. Grubbs, R.R. Schrock,
Mo, Ru
Nobel Prize for studies of catalysis in metathesis, 2005
G. Ertl
–
Nobel Prize for chemical processes on solid surfaces, 2007
Propylene oxide from propylene and hydrogen peroxide
Ti-zeolite
BASF, Evonik/Uhde, 2008
R.F. Heck, A. Suzuki, E. Negishi
–
Nobel Prize for cross-couplings in organic synthesis, 2010
TS-1 = titanium (iv) silicalite zeolite catalyst, MAO = methylaluminoxane, and HPPO = hydrogen peroxide to propylene oxide.
1.2 Mode of Action of Catalysts
The suitability of a catalyst for an industrial process depends mainly on the following three properties:
activity
selectivity
stability (deactivation behavior).
The question which of these functions is the most important is generally difficult to answer because the demands made on the catalyst are different for each process. First, let us define the above terms [5, 6, 7, 8].
1.2.1 Activity
Activity is a measure of how fast one or more reactions proceed in the presence of the catalyst. Activity can be defined in terms of kinetics or from a more practically oriented viewpoint. In a formal kinetic treatment, it is appropriate to measure reaction rates in the temperature and concentration ranges that will be present in the reactor.
The reaction rate r is calculated as the rate of change of the amount of substance nA of reactant A with time relative to the reaction volume or the mass of catalyst:
Kinetic activities are derived from the fundamental rate laws, for example, that for a simple irreversible reaction :
k is the rate constant and f (cA) is a concentration term that can exhibit a first-order or higher order dependence on adsorption equilibria (see Section 5.2).
The temperature dependence of rate constants is given by the Arrhenius equation:
where Ea is the activation energy of the reaction; k0 is the pre-exponential factor; and R is the gas constant.
Equations (1.2) and (1.3) show that there are three possibilities for expressing catalyst activity, which are as follows:
reaction rate
rate constant
k
activation energy
E
a
.
Empirical rate equations are obtained by measuring reaction rates at various concentrations and temperatures. If, however, different catalysts are to be compared for a given reaction, the use of constant concentration and temperature conditions is often difficult because each catalyst requires it own optimal conditions. In this case, it is appropriate to use the initial reaction rates r0 obtained by extrapolation to the start of the reaction.
Another measure of catalyst activity is the turnover number (TON), which originates from the field of enzymatic catalysis.
In the case of homogeneous catalysis, in which well-defined catalyst molecules are generally present in solution, the TON can be directly determined. For heterogeneous catalysts, this is generally difficult, because the activity depends on the size of the catalyst surface, which, however, does not have a uniform structure. For example, the activity of a supported metal catalyst is due to active metal atoms dispersed over the surface.
The number of active centers per unit mass or volume of catalyst can be determined indirectly by means of chemisorption experiments, but such measurements require great care, and the results are often not applicable to process conditions. Although the TON appears attractive due to its molecular simplicity, it should be used prudently in special cases.
In practice, readily determined measures of activity are often sufficient. For comparative measurements, such as catalyst screening, determination of process parameters, optimization of catalyst production conditions, and deactivation studies, the following activity measures can be used:
conversion under constant reaction conditions;
space velocity for a given, constant conversion;
space–time yield;
temperature required for a given conversion.
Catalysts are often investigated in continuously operated test reactors, in which the conversions attained at constant space velocity are compared [5].
The space velocity is the volume flow rate , relative to the catalyst mass mcat:
The conversion XA is the ratio of the amount of reactant A that has reacted to the amount that was introduced into the reactor. For a batch reactor,
If we replace the catalyst mass in Eq. (1.4) with the catalyst volume, then we see that the space velocity is proportional to the reciprocal of the residence time.
Often the performance of a reactor is given relative to the catalyst mass or volume, so that reactors of different size or construction can be compared with one another. This quantity is known as the space–time yield (STY):
Determination of the temperature required for a given conversion is another method of comparing catalysts. The best catalyst is the one that gives the desired conversion at a lower temperature. This method cannot, however, be recommended since the kinetics are often different at higher temperature, making misinterpretations likely. This method is better suited to carrying out deactivation measurements on catalysts in pilot plants.
1.2.1.1 Turnover Frequency TOF
The turnover frequency (TOF) (the term was borrowed from enzyme catalysis) quantifies the specific activity of a catalytic center for a special reaction under defined reaction conditions by the number of molecular reactions or catalytic cycles occurring at the center per unit time. For heterogeneous catalysts, the number of active centers is derived usually from sorption methods (Eq. (1.7)).
For most relevant industrial applications, the TOF is in the range 10−2–102 s−1 (enzymes 103–107 s−1).
Examples:
TOF values for the hydrogenation of cyclohexene at 25 °C and 1 bar (supported catalysts, structure-insensitive reaction) are provided in Table 1.2).
Metal
TOF (s
−1
)
Gas phase
Liquid phase
Ni
2.0
0.45
Rh
6.1
1.3
Pd
3.2
1.5
Pt
2.8
0.6
1.2.1.2 Turnover Number TON
The TON specifies the maximum use that can be made of a catalyst for a special reaction under defined conditions by a number of molecular reactions or reaction cycles occurring at the reactive center up to the decay of activity. The relationship between TOF and TON is (Eq. (1.8))
For industrial applications the TON is in the range 106–107.
1.2.2 Selectivity
The selectivity SP
