Nanostructured catalysts : selective oxidations

453 Pages·2011·99.092 MB·English

by  Christian Hess, Robert Schlögl

RSC Nanoscience & Nanotechnology
Edited by Christian Hess and Robert Schlögl
Nanostructured Catalysts
Selective Oxidations
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Nanostructured Catalysts
Selective Oxidations
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Nanostructured Catalysts
Selective Oxidations
Edited by
Christian Hess
Technische Universita¨t Darmstadt, Eduard-Zintl-Institut fu¨r Anorganische und
Physikalische Chemie, Petersenstr. 20, 64287 Darmstadt, Germany
and
Robert Schlo¨ gl
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Abteilung Anorganische
Chemie, Faradayweg 4–6, 14195 Berlin, Germany
RSCNanoscience&NanotechnologyNo.19
ISBN:978-0-85404-186-2
ISSN:1757-7136
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
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Preface
Heterogeneously catalyzed selective oxidation constitutes an important
area of chemical industry. A major application is the functionalization of
hydrocarbons leading to monomers or modifiers used for synthesis of
polymers. Within the area of selective catalytic oxidation the optimization
of selectivity is the most important goal. In fact, increasing sustainability by
preventing the formation of waste is of enormous relevance in large-scale
processes. However, despite extensive research over the last decades hetero-
geneously catalyzed selective oxidation reactions are still poorly understood
due to the complex interplay of processes in different scales of time and
length and the multitude of disciplines involved.
This book reviews recent developments in heterogeneously catalyzed
selective oxidation reactions with an emphasis on light hydrocarbons. Nano-
structuring is an important aspect of these catalysts. In fact, rational catalyst
design will heavily depend on the ability to control the catalysts structure and
particle size on the nanometer scale, strongly linking heterogeneous catalysis
with materials science. While a broad range of catalyst materials is covered, a
particular focus is placed on vanadium-containing catalysts because of their
importance for selective oxidation catalysis. To this end the effort is made to
merge the current state of knowledge into a consistent picture of the working
principle of selective oxidation catalysts.
This book gives a comprehensive up-to-date summary of the existing infor-
mation on heterogeneously catalyzed selective oxidation. Nonetheless, it is
not intended for specialists only. Graduate students and researchers both in
academia and industry from different areas of catalysis and different
background will receive an overview of the field, ranging from historical
developments to recent results, which should allow them to quickly catch up
with current research issues.
Thebookisorganizedasfollows.Chapter1givesashortintroductiontothe
fieldofselectiveoxidationanddiscussessomebasicaspectsofthereactionsand
RSCNanoscience&NanotechnologyNo.19
NanostructuredCatalysts:SelectiveOxidations
EditedbyChristianHessandRobertSchlo¨gl
rRoyalSocietyofChemistry2011
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
v
vi Preface
materialsthebookfocuseson.Chapter2dealswiththeinitialactivationstepof
C–H bonds in selective oxidation reactions on solid oxide catalysts. The first
section (Chapters 3–7) is dedicated to oxide-catalyzed selective oxidation
reactionsoflighthydrocarbonswithafocusonvanadiumand/ormolybdenum
containingcatalysts.Thenextseriesofchapters(Chapters8–11)coversselective
oxidation reactions over supported gold, (supported) silver, ruthenium oxide
and (potassium-promoted) iron-oxide catalysts. The next section (Chapters
12–14) addresses recent developments regarding supported vanadium-oxide
systems as well as mechanistic aspects of ethane/propane oxidative functiona-
lization. In Chapter 15 the characteristics of selective oxidation reactions are
discussed focusing on active sites of the V O type. Chapter 16 addresses
x y
engineeringaspectsofselectiveoxidationreactionswithreferencetoindustrial
processes.Chapter17givesashortoutlook.
Wehopethatthisbook,whilenotexhaustive,willgivethereaderanideaof
the fascinating field of selective oxidation catalysis. We feel that the field is
moving towards a profound scientific foundation that will offer plenty of
opportunities for better catalyst developments. We thank all contributors to
this book and we hope that you enjoy reading it.
Darmstadt and Berlin
Christian Hess
Robert Schlo¨gl
Contents
Chapter 1 Introduction 1
Christian Hess
References 3
Chapter 2 C–HActivationofAlkanes inSelective OxidationReactions
on Solid Oxide Catalysts 5
Johannes A. Lercher and Frederik N. Naraschewski
2.1 Introduction 5
2.2 Models of C–H Bond Activation over Supported and
Unsupported Oxide Clusters 7
2.2.1 Vanadium-Based Clusters 8
2.2.2 Molybdenum and Tungsten Oxide Clusters 12
2.2.3 Complex Mixed Oxides 14
2.2.4 Transition-Metal Species in Zeolites 16
2.3 Impact of Anions on C–H Activation 18
2.3.1 Vanadium Pyrophosphate as Catalyst for
Butane Activation 18
2.3.2 Supported LiCl as Catalyst for Oxidative
Dehydrogenation of Ethane to Ethene 20
2.4 Indirect Oxidation via Electrophilic Substitution –
Chlorination and Bromination 21
2.5 Oxidative C–H Activation via Activation with
Nonreducible Cations 24
2.5.1 C–H Activation of Alkanes by
Li-Promoted MgO 24
RSCNanoscience&NanotechnologyNo.19
NanostructuredCatalysts:SelectiveOxidations
EditedbyChristianHessandRobertSchlo¨gl
rRoyalSocietyofChemistry2011
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
viii Contents
2.5.2 Bifunctional Oxidative Catalysis with Main
Group Cations at Zeolite Exchange Sites 26
2.6 Conclusion and Outlook 27
References 28
Section I Oxide-Catalyzed Selective Oxidations of Light
Hydrocarbons (Chapters 3–7)
Chapter 3 Catalysis of Oxidative Methane Conversions 35
Evgenii V. Kondratenko and Manfred Baerns
3.1 Introduction 35
3.2 Methane as a Feedstock for Oxidative
Conversions 35
3.3 Oxidative Coupling of Methane (OCM) 37
3.3.1 Catalytic Materials and Modes of
Process Operation 37
3.3.2 Interaction of Methane on Solid
Catalytic Surfaces 38
3.3.3 Mechanistic Insights into Ethane,
Ethylene and CO Formation 39
x
3.3.4 Oxygen Species in the OCM Reaction 39
3.3.5 Selectivity- and Activity-Governing Factors 43
3.4 Methane Oxidation to Methanol and Formaldehyde 44
3.4.1 Interaction of Oxygen and Methane on
Transition-Metal Oxides 44
3.4.2 Methane to Methanol 45
3.4.2.1 Homogeneous and Heterogeneous
Methanol Formation 45
3.4.2.2 Enzymatic Conversion of Methane
to Methanol 47
3.4.3 Methane to Formaldehyde 48
3.5 Outlook 50
References 51
Chapter 4 Propane-Selective Oxidation to Acrylic Acid 56
Annette Trunschke
4.1 Introduction 56
4.2 Technological Background 57
4.3 Catalysts and Product Distribution in Selective
Oxidation of Propane 59
4.3.1 Phosphates 61
4.3.2 CatalystsDerivedfromHeteropolyCompounds 61
4.3.3 Multimetal Oxides 62
Contents ix
4.4 Crystal Structure of the Key Phases in
Mo-Based Multimetal-Oxide Catalysts 64
4.5 Phase Cooperation and Crystallinity 65
4.6 Synthesis of Phase-Pure Mo-Based Multimetal
Oxides 67
4.6.1 Preparation of Mo–V–Te–Nb Oxides by
Precipitation/Rapid Solvent
Evaporation 68
4.6.2 Preparation of Mo–V–Te–Nb Oxides by
Hydrothermal Synthesis 71
4.7 Characteristics of M1 74
4.7.1 Reaction Network and Mechanism 74
4.7.2 Chemical Composition and Active Sites 78
4.7.3 Structure Sensitivity and Termination 79
4.7.4 Surface Dynamics 82
4.8 Functional Model of M1 84
Acknowledgements 86
References 87
Chapter 5 Ammoxidation of Propylene and Propane to
Acrylonitrile 96
Robert K. Grasselli
5.1 Introduction and Historic Background 96
5.2 General 99
5.3 Propylene Ammoxidation to Acrylonitrile 100
5.3.1 The SOHIO Acrylonitrile Process 101
5.3.2 Key Catalytic Functionalities 104
5.3.3 Role of Lattice Oxygen – Catalyst as
Redox Solid 104
5.3.4 Generalized Mechanism of Alkene
Ammoxidation 106
5.3.5 Multifunctional Nature of Active Sites 106
5.3.6 Ammoxidation Mechanism (Molybdates,
Antimonates) 108
5.3.7 Molybdate Catalysts 113
5.3.8 Multicomponent Molybdates 114
5.3.9 Commercial Molybdate Catalysts 116
5.3.10 Antimonate Catalysts 119
5.4 Propane Ammoxidation to Acrylonitrile 122
5.4.1 Structure of MoVNbTeO Catalysts 124
5.4.2 Symbiosis between M1 and M2 Phases 126
5.4.3 Reaction Network and Mechanism 130
5.4.4 Future Research 135
References 136