Encompassing an integrated approach to the various aspects of catalysis, covering heterogeneous, homogeneous, organo-, bio-, and computational catalysis, as well as reaction and reactor engineering on an advanced level, this textbook is ideal for graduate students with diverse backgrounds, including catalysis, engineering, and organic synthesis. The basic principles of the various fields of catalysis are introduced in a concise way, preparing the reader for the more advanced chapters. Organometallic chemistry, surface science, biochemistry, nanoscience, transport phenomena and kinetics, reactor and reaction engineering are presented, spanning from the underlying science to industrial applications. Several important case studies on industrial applications are given. It includes catalyst preparation and characterisation and explores recent developments in the understanding of catalytic mechanisms, exploring advanced techniques such as operando spectroscopy.
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Paul C J Kamer is a Professor at the University of St Andrews, Scotland. His research focuses on homogeneous catalysis with an emphasis on the synthesis of phosphorus donor ligands by rational design assisted by molecular modelling.
Dieter Vogt is a Professor at the University of Edinburgh. Scotland. His research interests cover homogeneous catalysis, catalyst recycling, mechanistic studies, ligand design and sustainable chemistry.
Joris Thybaut is a Professor at Ghent University, Belgium. His research interests are in catalytic reaction engineering with a focus on kinetics and reactors.
Encompassing an integrated approach to the various aspects of catalysis, covering heterogeneous, homogeneous, organo-, bio-, and computational catalysis, as well as reaction and reactor engineering on an advanced level, this textbook is ideal for graduate students with diverse backgrounds, including catalysis, engineering, and organic synthesis.
The basic principles of the various fields of catalysis are introduced in a concise way, preparing the reader for the more advanced chapters. Organometallic chemistry, surface science, biochemistry, nanoscience, transport phenomena and kinetics, reactor and reaction engineering are presented, spanning from the underlying science to industrial applications. Several important case studies on industrial applications are given. It includes catalyst preparation and characterisation and explores recent developments in the understanding of catalytic mechanisms, exploring advanced techniques such as operando spectroscopy.
Encompassing an integrated approach to the various aspects of catalysis, covering heterogeneous, homogeneous, organo-, bio-, and computational catalysis, as well as reaction and reactor engineering on an advanced level, this textbook is ideal for graduate students with diverse backgrounds, including catalysis, engineering, and organic synthesis.
The basic principles of the various fields of catalysis are introduced in a concise way, preparing the reader for the more advanced chapters. Organometallic chemistry, surface science, biochemistry, nanoscience, transport phenomena and kinetics, reactor and reaction engineering are presented, spanning from the underlying science to industrial applications. Several important case studies on industrial applications are given. It includes catalyst preparation and characterisation and explores recent developments in the understanding of catalytic mechanisms, exploring advanced techniques such as operando spectroscopy.
Section I Introduction,
1 History of Catalysis Jacob A. Moulijn and Rutger A. van Santen,
2 Feedstocks and Renewable Resources Johannes G. de Vries, Peter J. Deuss and Katalin Barta,
3 Current Challenges in Catalysis Dieter Vogt and Nicholas J. Westwood,
Section II Underlying Principles for Catalysis,
4 Organometallic Chemistry and Elementary Steps Piet W. N. M. van Leeuwen,
5 Nanoscience Christopher J. Baddeley,
6 An Introduction to Biocatalysis R. Wever, R. J. M. Goss, E. Spence, Xiaoxue Tong and A. F. Hartog,
7 Thermodynamics and Kinetics Nicole Wilde and Roger Gläser,
Section III Fundamental Catalysis,
8 Heterogeneous Catalysis Harry Bitter,
9 Homogeneous Catalysis Dieter Vogt,
10 Organocatalysis Daniel G. Stark and Andrew D. Smith,
11 Biocatalysis R. Wever, M. J. Corr, R. J. M. Goss and Paul Kamer,
12 Computational Catalysis Stuart A. Macgregor, Michael Bühl and Emiel J. M. Hensen,
13 Introduction to Electrocatalysis John T. S. Irvine,
14 Photocatalysis Akihiko Kudo,
Section IV Catalyst Preparation,
15 Solid Materials for Heterogeneous Catalysis Nicole Wilde and Roger Gläser,
16 Transition Metal Complexes and Ligand Synthesis David J. Nelson and Steven P. Nolan,
17 Organocatalysts Aileen B. Frost, Mark D. Greenhalgh and Andrew D. Smith,
18 Enzymes for Biocatalysis: Key Concepts, Engineering Principles and Case Studies Guiomar Sánchez-Carrón and Dominic J. Campopiano,
Section V Catalyst Characterization,
19 Advanced Solution Spectroscopic Techniques Jonathan A. Iggo and Alice Parry,
20 X-Ray Photoelectron Spectroscopy Adam F. Lee, Christopher M. A. Parlett and Karen Wilson,
21 Bulk X-Ray Techniques Adam F. Lee, Christopher M. A. Parlett and Karen Wilson,
22 Adsorption Methods Adam F. Lee, Christopher M. A. Parlett and Karen Wilson,
23 Temperature Programmed Techniques Adam F. Lee, Christopher M. A. Parlett and Karen Wilson,
Section VI Operando Techniques,
24 Operando Techniques M. Bauer, U. Bentrup, J. B. Priebe and A. Brückner,
Section VII Reaction and Reactor Engineering,
25 Reaction and Reactor Engineering Jeroen Lauwaert, Joris W. Thybaut, Alexandre Goguet, Christopher Hardacre, Oluwafunmilola Ola and Mercedes Maroto-Valer,
Section VIII Separation,
26 Catalyst Separation Robert Konrath, Frank J. L. Heutz, Paul C. J. Kamer and Dieter Vogt,
Section IX Process Intensification,
27 Process Intensification in Catalysis Sebastian Falß, Martin Rieks and Norbert Kockmann,
Section X Industrial Processes,
28 Transition Metal Catalysed Methanol Carbonylation Anthony Haynes,
Section XI Life Cycle Analysis,
29 Environmental Analyses and Life Cycle Assessment Studies Dana Kralisch and Denise Ott,
Subject Index,
History of Catalysis
Jacob A. Moulijn and Rutger A. van Santen,
1.1 History of Catalysis – Introduction
Without catalysis, life is not possible and, in that sense, catalysis is as old as life. The oldest catalytic processes used by humans are the production of wine, beer, alcohol and acetic acid, all through the fermentation of carbohydrates. This technology was already practised earlier than 2000 years BC. Compared to biocatalysts, the utilisation of chemocatalysts in industrial production is recent. Over the years, catalysis has developed into a broad discipline. History includes a wealth of theories and achievements that have changed society. Since catalysis as a whole is a topic too broad, we will not try to completely cover all historic developments. We will mention the numerous successful multicomponent catalyst systems as a chronological list presented in a table. In this chapter, the history of catalysis will be presented with a flavour of practical applications and a focus on heterogeneous (chemo)catalysis.
The name 'catalysis' was coined by Berzelius in 1836. He concluded that besides 'affinity', a new force was operative, a 'Catalytic Force'. The word 'catalysis' stems from the Greek: ?ata??s?, which means loosening, allow to move downwards freely. In the time of Berzelius, the term 'affinity' was used; however, on a molecular level, no understanding existed of reaction rates. Although insight was limited, catalysis as a new tool was booming.
When we limit ourselves to catalytic production processes of chemicals, the first commercial application was the production of sulphuric acid in the mid-18th century. The history of the production of sulphuric acid is interesting. In the Middle Ages, it was synthesised in the laboratory in glass equipment by burning sulphur with nitric acid in humid air. In 1746, lead was introduced as a construction material and the so-called lead chamber process allowed commercial production. In 1793, Clément and Desormes discovered that the quantity of nitric acid could be reduced if additional air was provided: a catalytic process was born. They realised that SO2 was converted into SO3 by air and that nitrous vapours were not consumed in a stoichiometric reaction but they were only intermediates. Remarkably, this process was a homogeneously catalysed process: in aqueous solution, SO2 is oxidised to sulphuric acid with nitrogen oxides functioning as O-transfer agents. A specific characteristic of the process is that, at high sulphuric acid concentrations, stable nitrosyl sulfate compounds are formed making it impossible to produce sulphuric acid in high concentration and purity. As early as 1831, a process was patented in which the oxidation was catalysed by a solid catalyst, Pt, allowing the production of the generally desired concentrated sulphuric acid. A commercial application, however, was strongly delayed due to practical difficulties, the major one being the low stability of the catalyst. It should be noted that elemental sulphur was initially the raw material. Later, pyrite was used because of its lower price. However, processing of pyrite ore was associated with considerable amounts of impurities, which acted as catalyst poisons. Not surprisingly, the Pt crystals were more sensitive to poisons than nitrogen oxides. This is a major reason why it took so long before a heterogeneously catalysed process became feasible. Nowadays, all processes for the production of sulphuric acid are heterogeneous. Vanadium-based catalysts have largely replaced Pt catalysts as they are cheaper and less susceptible to poisoning. Vanadium is present as a liquid salt in the pores of a porous solid carrier. At present, the raw material for the production of sulphuric acid is mainly elemental sulphur again, strongly reducing the catalyst deactivation. Sulphur is not expensive as it is a by-product from the hydrotreatment of oil fractions.
Around the turn of the 18th century, the influence of metal and metal oxides on decomposition reactions was a hot topic. An example is the decomposition of ethanol. In the presence of copper or iron, carbon and a 'flammable gas' were produced, whereas in the presence of pumice stone, ethene and water were observed. In retrospect, catalyst selectivity was demonstrated.
Good insight into the struggle to find an interpretation of observed reaction rates is given by the work...
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