Table Of ContentA Specialist Periodical Report
Catalysis
Volume 12
A Review of Recent Literature
Senior Reporter
James J. Spivey, Center for Process Research, Research
Triangle Institute, Research Triangle Park, North Carolina, USA
Reporters
M. Ai, Niigata lnstitute of Technology, Kashiwazaki, Japan
Burtron H. Davis, University of Kentucky, Lexington, Kentucky, USA
Koic h i Eg u c hi , Kyus h u University, Fu kuo ka, Japan
Gyorgy Horanyi, Hungarian Academy of Sciences, Budapest, Hungary
Manjula M. Ibrahim, West Virginia University, Morgantown, West
Virginia, USA
Tatsumi Ishihara, Oita University, Oita, Japan
Shigemi Mandai, Mitsubishi Heavy Industries Ltd, Taskasago, Japan
Toshio Matsuhisa, Calalysts & Chemicals lnc, Tokyo, Japan
Stylianos G. Neoph ytides, University of Patras, Patras, Greece
Ajoy Raje, University of Kentucky, Lexington, Kentucky, USA
Mohindar S. Seehra, West Virginia University, Morgantown, West
Virginia, USA
Yusa ku Takita, Oita University, Oita, Japan
Constantinos G. Vayenas, University of Patras, Patras, Greece
THE ROYAL
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ISBN 0-85404-204-0
0 The Royal Society of Chemistry 1996
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Preface
The completion of Volume 12 in the Catalysis series has been especially rewarding.
I have continued a conscious effort to cover a wide range of subjects in our field. More
publications in catalysis are available each year, reflecting a healthy interest in catalysis
as an important tool with which to address concerns in environment control, energy
conversion processes, and synthesis of chemicals. The chapters presented to you here deal
with these areas, as well as the more fundamental analytical methods and material
synthesis.
Dr. Matsuhisa presents a review of the nature of Cu-ZnO catalysts, which are
widely used for the industrially important synthesis of methanol. Despite the importance
of these materials, there have been relatively few reviews on the mechanism and the
review presented here attempts to add to our knowledge of this reaction.
Drs. Ishihara and Takita focus on a specific catalyst, the aluminophosphate
molecular sieves. These materials have some useful properties that distinguish them from
the more widely used aluminosilicates. These include generally milder acidity, somewhat
different ion exchange properties, and higher thermal stability. This allows them to be
used in a number of reactions in which aluminosilicates are not suitable, such as low-
temperature catalytic combustion.
Drs. Raje and Davis present interesting work on the use of isotopes to study
Fischer-Tropsch synthesis. This route to synthetic chemicals, despite having been studied
for some time, must be more cost-competitive before it will be widely used. The work
presented in this chapter will help us understand the mechanism of the reactions and how
to maximize yields.
Dr. Eguchi presents a review of catalysts used for high-temperature catalytic
combustion. This process offers the possiblity of greatly reducing NO, emissions from gas
turbines, but there is considerable work needed to develop materials that have both the
low-temperature activity and durability at 1,200 to 1,400 "C to be of practical interest.
This review summarizes the most recent research in this area.
Dr. Ai reviews the condensation of formaldehyde and methanol with other
hydrocarbons to form the widely used vinyl compounds, such as methacrylic acid and
methyl methacrylate. The development of active and stable solid catalysts for these
reactions can eliminate the significant environmental problems faced with the current
industrial routes to these chemicals.
Drs. Vayenas and Neophytides present a thorough review of electrochemical activa-
tion of catalysts. This process can be used in situ to control the catalytic process and
improve selectivity and yield for certain reactions. This is especially important as new
iv Carulysis
solid ion conducting electrolytes with better thermal stability and ion conductivity are
developed.
Dr. Horinyi reviews a fundamental area of electrocatalysis, one in which there is
a solid-fluid boundary. He presents a thorough review of the key parameters in this field
and provides background information and nomenclature for the uninitiated.
Drs. Seehra and Ibrahim summarize recent advances in the important analytical tool
of electron spin resonance, particularly as it is used in the direct catalytic liquefaction of
coal. This tool is especially important because it can now be used in situ. There is some
question about the role of free radicals in direct liquefaction, and the authors explore this
subject.
Finally, Dr. Mandai presents a summary of the use of theoretical analysis of
catalytic combustion as used in gas turbines. This allows the understanding of the
processes occurring at conditions that are difficult to reproduce in the laboratory, but which
are extremely important at conditions of practical interest.
I have appreciated the efforts of the authors and reviewers in meeting the schedule
we set for ourselves. I also wish to thank the Royal Society of Chemistry for their support
of the series. The thoroughness and attention to detail of Ms. Jan Shirley and Ms. Linda
Gaydosh of RTI’s Publication and Design Services are evident in the presentation of the
book, which is prepared entirely from camera-ready mats. They deserve more credit than
I am able to give them here.
James J. Spivey
Research Triangle Institute
Research Triangle Park, NC USA
Contents
Chapter 1 Structure of Active Sites of Cu-ZnO Catalysts and
Selective Formation of Relevant Precursors 1
By Toshio Matsuhisa
1 Introduction 1
2 Nature of Active Sites 2
2.1 Structure of Active Sites 2
2.2 The Role of ZnO 3
2.3 Relation Between Oxygen Coverage and Activity of
Methanol Synthesis 4
3 Selective Formation of Precursors and Their Structures 6
3.1 Addition Rates and Obtained Precursors 7
3.2 Effect of Concentration of NaHCO, Solution on the
Distribution of Precursors 8
3.3 Nature of Initial Intermediates and Precursors 8
3.4 Mechanism of Precursor 'Formation 10
4 Prospect for the Improvement of Methanol Synthesis Catalysts 12
4.1 Increasing Activity by Achieving Highly Dispersed
Copper 13
4.2 Effect of Support on Cu Surface Area and Methanol
Synthesis Activity 15
5 summary 18
Acknowledgment 19
References 20
Chapter 2 Property and Catalysis of Aluminophosphate-b ased
Molecular Sieves 21
By Tatsumi Ishihara and Yusaku Takita
1 Introduction 21
2 Crystallite Structure of AIPO-n 22
vi Catalysis
3 Metal-aluminophosphate (MeAPO-n) and Silico-
aluminophosphate (SAPO) 24
3.1 Isomorphous Substitution of AlPO with Metal Cations 24
3.2 Solid Acidity of SAPO-n and MeAPO-n 28
3.3 Ion-Exchange Sites in AlPO-n-Based Molecular Sieves 32
4 Catalysis of AlPO-n, MeAPO-n, or SAPO-n as a Solid Acid 33
5 Aluminophosphate-based Molecular Sieves as a Thermostable
Catalyst 36
5.1 Thermal Stability of Aluminophosphate-based
Molecular Sieves 37
5.2 Application of Aluminophosphate- based Molecular
Sieves for a Thermostable Catalyst 39
5.2.1 Thermostable NO Reduction Catalyst with
I
Hydrocarbon 40
5.2.2 Application of SAPO-5 Ion-Exchanged with Pd for
Combustion Catalyst 44
6 Conclusion 49
References 49
Chapter 3 Fischer-Tropsch Synthesis. Mechanism Studies Using Isotopes 52
By Ajoy Raje uizd Burtron H. Duvis
1 Introduction 52
2 Is Bulk Carbide an Intermediate? 53
3 Heterogeneity of the Catalyst Surface 55
4 Irreversibility of the Chain Growth Process 56
5 Studies with Labelled Molecules 60
5.1 Dissociation of CO 60
5.2 Iron Catalysts 61
5.3 Synthesis with Co Catalysts 86
5.4 Ruthenium Catalysts 98
5.5 Other Metals 101
6 Kinetic Isotope Effect 102
7 Water-Gas Shift 109
Cont ents vii
8 Isotope Transient Kinetic Studies 115
8.1 Nature of Adsorbed Species 117
8.2 Transient Isotopic Kinetic Studies of Methanation 119
8.3 Isotopic Transient Kinetic Studies of the FTS 121
Acknowledgment 127
References 127
Chapter 4 Catalyst Materials for High-temperature Combustion 132
By Koichi Eguchi
1 Introduction 132
2 Reaction Characteristics for Catalytic Combustion 133
3 Catalyst Materials for High-temperature Combustion 135
3.1 Structure of Honeycomb Catalysts 135
3.2 Thermal Stability of Catalysts 136
3.3 Thermal Shock Resistance 138
4 Analysis of Sintering Behavior of Hexaaluminate 139
5 - The Active Component for Combustion Reaction 141
6 Activity of Pd Catalyst for Methane Combustion 145
7 Application of Catalytic Combustion to Gas Turbines 147
8 Conclusion 150
Acknowledgment 150
References 150
Chapter 5 Vapor Phase Condensation Reactions Using Formaldehyde
or Methanol 152
By M. Ai
1 Introduction 152
2 Acid-Base Properties of Metal Oxides 152
Viii Catalysis
3 Reaction of HCHO with Carboxylic Acids 154
3.1 Catalysts 154
3.2 Reaction of HCHO with Acetic Acid 154
3.2.1 Reaction over Base Catalysts 154
3.2.2 Reaction over Acid Catalysts 156
3.3 Reaction of HCHO with Propionic Acid 159
3.3.1 Reaction over Base Catalysts 161
3.3.2 Reaction over Acid Catalysts 161
4 Reaction of HCHO with Alkyl Esters of Carboxylic Acids 163
4.1 Catalysts 164
4.2 Reactiqn of HCHO with Methyl Acetate 164
4.2.1 Reaction over Base Catalysts 164
4.2.2 Reaction over Acid Catalysts 164
4.3 Reaction of HCHO with Methyl Propionate 166
4.3.1 Reaction over Base Catalysts 166
4.3.2 Reaction over Acid Catalysts 169
5 Reaction of Methanol with Acids or Esters 171
5.1 Reaction in the Presence of Oxygen 171
5.1.1 Reaction of Methyl Acetate. 171
5.1.2 Reaction with Methyl Propionate 175
5.2 Reaction of Methanol in the Absence of Oxygen 175
6 Reaction with Nitriles 178
6.1 Reaction of HCHO with Nitriles 178
6.2 Reaction of Methanol with Nitriles 179
7 Reaction with, Carbonyl Compounds 181
7.1 Reaction of HCHO with Aldehydes 181
7.2 Reaction of HCHO with Ketones 187
7.3 Reaction of Methanol with Carbonyl Compounds 189
8 Reaction of HCHO with Alcohols 190
9 Other Related Reactions 193
10 Conclusion 193
References 196
