This reference book addresses the evolution of materials for both oxygen and hydrogen transport membranes and offers strategies for their fabrication as well as their subsequent incorporation into catalytic membrane reactors. Other chapters deal with, e.g., engineering design and scale-up issues, strategies for preparation of supported thin-film membranes, or interfacial kinetic and mass transfer issues. A must for materials scientists, chemists, chemical engineers and electrochemists interested in advanced chemical processing.

Anthony F. Sammells received his B.S. in Chemistry from the University of London. After working as a technical supervisor for the Crown Zellerback Co. in Portland, Oregon he obtained his Ph.D. in inorganic chemistry (electrochemistry) from the University of California at Santa Barbara. After this, he was developmental engineer at Information Magnetics in Santa Barbara, California, until he moved to the Energy Research Division of Gould Laboratories, St. Paul, Minnesota. After an employment in the MTS Atomics International Division of Rockwell International, Canoga Park, California, he was Assistant Director of Solar and Electrochemistry Research at the Institute of Gas Technology, Chicago, Illinois. Today Dr. Sammells has responsibility for directing research at Eltron Research Inc. in Boulder, Colorado. He is a member of the American Chemical Society, the Electrochemical Society and Sigma Xi. He has over one hundred publications and over fifty patents.

Michael V. Mundschau studied chemistry at the University of Wisconsin. His Ph.D studies were in catalysis and surface science at the Laboratory for Surface Studies. Studies continued on the fundamentals of thin-film growth using low-energy electron microscopy (LEEM) and photoelectron emission microscopy (PEEM) as an Alexander von Humboldt fellow at the Institute of Physics in Clausthal-Zellerfeld, Germany. He continued studies of catalytic reactions and reaction-diffusion fronts at the Fritz-Haber-Institute in Berlin, before returning to the United States for a teaching position at Bowling Green State University, where surface studies using PEEM were continued. He also spent time at the University of Illinois at Urbana-Champaign studying buried interfaces and thin-film growth using LEEM. He has been working at Eltron Research Inc. to develop membrane catalysts and catalyst deposition techniques for oxygen and hydrogen transport membranes. Michael Mundschau is the author of over 45 scientific papers, and has presented his work as invited speaker at over 60 conferences and seminars around the world.

Preface	p. XI
List of Contributors	p. XIII
Dense Ceramic Membranes for Hydrogen Separation	p. 1
Introduction	p. 1
Applications and Principles of Operation	p. 2
Simple Cases	p. 2
Examples of More Complex Applications	p. 4
Defect Chemistry of Dense Hydrogen-permeable Ceramics	p. 5
Materials Classes	p. 5
Neutral and Ionized Hydrogen Species in Oxides	p. 6
Protonic Defects and Their Transport	p. 7
Defect Structures of Proton-conducting Oxides	p. 8
Diffusivity, Mobility and Conductivity: The Nernst-Einstein Relation	p. 10
Wagner Transport Theory for Dense Ceramic Hydrogen-Separation Membranes	p. 11
General Expressions	p. 11
From Charged to Well-Defined Species: The Electrochemical Equilibrium	p. 12
The Voltage Over a Sample	p. 12
Flux of a Particular Species	p. 13
Fluxes in a Mixed Proton, Oxygen Ion, and Electron Conductor	p. 14
Fluxes in a Mixed Proton and Electron Conductor	p. 15
Fluxes in a Mixed Proton and Oxygen Ion Conductor	p. 18
Fluxes in a Mixed Proton, Oxygen Ion, and Electron Conductor Revisited	p. 19
Permeation of Neutral Hydrogen Species	p. 19
What About Hydride Ions?	p. 21
Surface Kinetics of Hydrogen Permeation in Mixed Proton-Electron Conductors	p. 21
Issues Regarding Metal Cation Transport in Hydrogen-permeable Membrane Materials	p. 24
Modeling Approaches	p. 24
Experimental Techniques and Challenges	p. 26
Investigation of Fundamental Materials Properties	p. 26
Concentration	p. 26
Diffusion	p. 27
Conductivity	p. 27
Transport Numbers	p. 29
Other Properties	p. 30
Investigation of Surface Kinetics	p. 31
Measurements and Interpretation of Hydrogen Permeation	p. 34
Hydrogen Permeation in Selected Systems	p. 35
A Few Words on Flux and Permeability	p. 35
Classes of Membranes	p. 36
Mixed Proton-Electron Conducting Oxides	p. 36
Cermets	p. 42
Permeation in Other Oxide Classes and the Possibility of Neutral Hydrogen Species	p. 43
Comparison with Metals	p. 44
Summary	p. 45
Ceramic Proton Conductors	p. 49
Introduction	p. 49
General properties of Perovskite-structured Proton-conducting Ceramic Membranes	p. 51
Creation of Protonic Carriers	p. 51
Transport Properties	p. 52
Electronic Conductivity and Its Improvement	p. 57
Synthesis of Proton-conducting Ceramic Membranes	p. 58
Synthesis of Powders	p. 58
Effect of Synthesis Conditions on Membrane Performance	p. 59
Preparation of Thin Films	p. 60
Hydrogen Permeation	p. 61
The H[subscript 2] Permeation Set-up and Sealing System	p. 61
Effects of Process Variables on H[subscript 2] Flux	p. 63
Effect of Feed and Sweep Side Gas Concentrations	p. 63
Effect of Membrane Thickness	p. 64
Effect of Temperature	p. 65
Mathematical Models for Hydrogen Permeation	p. 66
Chemical Stability of Protonic Conductors	p. 68
Stability in C0[subscript 2] Atmospheres	p. 68
Stability in Moisture-containing Atmospheres	p. 71
Stability in Reducing Atmospheres	p. 71
Future Directions and Perspectives	p. 72
Palladium Membranes	p. 77
Introduction	p. 77
History and Applications	p. 78
Effect of Impurities	p. 79
Palladium Alloy Membranes	p. 81
Palladium Deposition Methods	p. 82
Membrane Characterization and Analysis	p. 84
Palladium Composite Membranes	p. 87
Recent Advances	p. 89
Summary and Outlook	p. 93
Superpermeable Hydrogen Transport Membranes	p. 107
Introduction	p. 107
Theoretical Limits of Superpermeable Membranes	p. 109
Superpermeable Membranes in Plasma Physics	p. 111
Hydrogen Transport Membranes in Nuclear Reactor Cooling Systems	p. 112
Hydrogen Transport Membranes in the Chemical Industry	p. 114
Membrane Hydrogen Dissociation Catalysts and Protective Layers	p. 116
Thermal and Chemical Expansion	p. 119
Methods of Catalyst Application	p. 121
Catalyst Tolerance to Sulfur	p. 124
Interdiffusion	p. 125
Measured Hydrogen Permeability of Bulk Membrane Materials	p. 126
Conclusions	p. 136
Engineering Scale-up for Hydrogen Transport Membranes	p. 139
Historical Review	p. 140
General Review of Hydrogen-permeable Metal Membranes and Module Design	p. 141
Scale-up and Differential Expansion	p. 142
Overview of Sealing Methods	p. 146
Scale-up from Laboratory Test-and-Evaluation Module to Commercial Membrane Module	p. 147
Cost and Membrane Thickness	p. 149
Module Maintenance and Operating Costs	p. 152
Overview of Membrane Fabrication Methods	p. 152
Membrane Module Design and Construction	p. 153
Design of the Module Shell	p. 159
Membrane Sealing Options	p. 160
Commercial Applicability	p. 163
The Evolution of Materials and Architecture for Oxygen Transport Membranes	p. 165
Introduction	p. 165
Oxygen Separation and Collection	p. 165
Background for Selection of Materials for Oxygen Separation and Collection	p. 166
Membrane Materials Concepts	p. 168
Membrane Architecture Concepts	p. 174
Summary of Oxygen Separation Materials and Architecture	p. 180
Syngas Production and Combustion Applications	p. 180
Background for Selection of Materials for Syngas Production and Combustion Applications	p. 180
Membrane Materials Concepts	p. 182
Membrane Architecture Concepts	p. 183
Summary of Syngas and Combustion Applications Materials and Architecture	p. 184
Membranes for Promoting Partial Oxidation Chemistries	p. 185
Introduction	p. 185
On the Nature of Perovskite-related Metal Oxides for Achieving Mixed Oxygen Anion and Electron Conduction	p. 188
Background	p. 188
Early Work towards the Selection of Mixed Conductors	p. 189
Requirements for Oxygen Anion and Electronic Conduction within Perovskites	p. 189
Empirical Factors Relating to Oxygen Anion Transport in Perovskite-related Membranes	p. 191
Introducing Electronic Conductivity into a Perovskite-related Lattice	p. 192
The Application of Oxygen Transport Membranes to Partial Oxidation Chemistries	p. 193
Natural Gas Conversion to Synthesis Gas - General Considerations	p. 193
Methane Partial Oxidation to Synthesis Gas in Membrane Reactors	p. 196
Liquid Fuel Reforming	p. 198
Coal/Biomass to Synthesis Gas	p. 200
Oxygen Reduction Catalysis Requirements in Oxygen Transport Membranes	p. 202
Methane to Ethylene	p. 203
Catalysis Considerations for Promoting Methane Coupling Reactions	p. 204
Catalyst Implementation on Dense Oxygen Transport Media for Oxidative Coupling	p. 206
Alkane Dehydrogenation	p. 206
Hydrogen Sulfide Partial Oxidation	p. 207
Some Thoughts on the Potential Contribution of Membrane Technology towards Realizing a Hydrogen Economy	p. 209
Syngas Membrane Engineering Design and Scale-Up Issues. Application of Ceramic Oxygen Conducting Membranes	p. 215
Membrane Design and Engineering	p. 216
Reactor Design and Engineering	p. 227
Planar Membrane Reactors	p. 232
Ceramic-to-Ceramic Seals	p. 235
Ceramic-to-Metal Seals	p. 238
Summary and Conclusions	p. 241
Economics Associated with Implementation of Membrane Reactors	p. 245
Introduction	p. 245
Membrane Reactors	p. 246
Factors Influencing the Economics	p. 249
Dense Membrane Reactors for the Water-Gas Shift Reaction	p. 251
Economic Feasibility of Water-Gas Shift Pd-based Membrane Reactors	p. 256
Future Directions	p. 261
Index	p. 265
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