Nonporous Inorganic Membranes – For 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.List of Contributors.1 Dense Ceramic Membranes for Hydrogen Separation (Truls Norby and Reidar Haugsrud).1.1 Introduction.1.2 Applications and Principles of Operation.1.2.1 Simple Cases.1.2.2 Examples of More Complex Applications.1.3 Defect Chemistry of Dense Hydrogen-permeable Ceramics.1.3.1 Materials Classes.1.3.2 Neutral and Ionized Hydrogen Species in Oxides.1.3.4 Protonic Defects and Their Transport.1.3.5 Defect Structures of Proton-conducting Oxides.1.3.6 Diffusivity, Mobility and Conductivity: The Nernst-Einstein Relation.1.4 Wagner Transport Theory for Dense Ceramic Hydrogen-Separation Membranes.1.4.1 General Expressions.1.4.2 From Charged to Well-Defined Species: The Electrochemical Equilibrium.1.4.3 The Voltage Over a Sample.1.4.4 Flux of a Particular Species.1.4.5 Fluxes in a Mixed Proton, Oxygen Ion, and Electron Conductor.1.4.6 Fluxes in a Mixed Proton and Electron Conductor.1.4.7 Fluxes in a Mixed Proton and Oxygen Ion Conductor.1.4.8 Fluxes in a Mixed Proton, Oxygen Ion, and Electron Conductor Revisited.1.4.9 Permeation of Neutral Hydrogen Species.1.4.10 What About Hydride Ions?1.5 Surface Kinetics of Hydrogen Permeation in Mixed Proton-Electron Conductors.1.6 Issues Regarding Metal Cation Transport in Hydrogen-permeable Membrane Materials.1.7 Modeling Approaches.1.8 Experimental Techniques and Challenges.1.8.1 Investigation of Fundamental Materials Properties.1.8.1.1 Concentration.1.8.1.2 Diffusion.1.8.1.3 Conductivity.1.8.1.4 Transport Numbers.1.8.1.5 Other Properties.1.8.2 Investigation of Surface Kinetics.1.8.3 Measurements and Interpretation of Hydrogen Permeation.1.9 Hydrogen Permeation in Selected Systems.1.9.1 A Few Words on Flux and Permeability.1.9.2 Classes of Membranes.1.9.3 Mixed Proton-Electron Conducting Oxides.1.9.4 Cermets.1.9.5 Permeation in Other Oxide Classes and the Possibility of Neutral Hydrogen Species.1.9.6 Comparison with Metals.1.10 Summary.2 Ceramic Proton Conductors (Vineet K. Gupta and Jerry Y. S. Lin).2.1 Introduction.2.2 General Properties of Perovskite-structured Proton-conducting Ceramic Membranes.2.2.1 Creation of Protonic Carriers.2.2.2 Transport Properties.2.2.3 Electronic Conductivity and Its Improvement.2.3 Synthesis of Proton-conducting Ceramic Membranes.2.3.1 Synthesis of Powders.2.3.2 Effect of Synthesis Conditions on Membrane Performance.2.3.3 Preparation of Thin Films.2.4 Hydrogen Permeation.2.4.1 The H2 Permeation Set-up and Sealing System.2.4.2 Effects of Process Variables on H2 Flux.2.4.2.1 Effect of Feed and Sweep Side Gas Concentrations.2.4.2.2 Effect of Membrane Thickness.2.4.2.3 Effect of Temperature.2.4.3 Mathematical Models for Hydrogen Permeation.2.5 Chemical Stability of Protonic Conductors.2.5.1 Stability in CO2 Atmospheres.2.5.2 Stability in Moisture-containing Atmospheres.2.5.3 Stability in Reducing Atmospheres.2.6 Future Directions and Perspectives.3 Palladium Membranes (Stephen N. Paglieri).3.1 Introduction.3.2 History and Applications.3.3 Effect of Impurities.3.4 Palladium Alloy Membranes.3.5 Palladium Deposition Methods.3.6 Membrane Characterization and Analysis.3.7 Palladium Composite Membranes.3.8 Recent Advances.3.9 Summary and Outlook.4 Superpermeable Hydrogen Transport Membranes (Michael V. Mundschau, Xiaobing Xie, and Carl R. Evenson IV).4.1 Introduction.4.2 Theoretical Limits of Superpermeable Membranes.4.3 Superpermeable Membranes in Plasma Physics.4.4 Hydrogen Transport Membranes in Nuclear Reactor Cooling Systems.4.5 Hydrogen Transport Membranes in the Chemical Industry.4.6 Membrane Hydrogen Dissociation Catalysts and Protective Layers.4.7 Thermal and Chemical Expansion.4.8 Methods of Catalyst Application.4.9 Catalyst Tolerance to Sulfur.4.10 Interdiffusion.4.11 Measured Hydrogen Permeability of Bulk Membrane Materials.4.12 Conclusions.5 Engineering Scale-up for Hydrogen Transport Membranes (David J. Edlund).5.1 Historical Review.5.2 General Review of Hydrogen-permeable Metal Membranes and Module Design.5.2.1 Scale-up and Differential Expansion.5.2.2 Overview of Sealing Methods.5.3 Scale-up from Laboratory Test-and-Evaluation Module to Commercial Membrane Module.5.3.1 Cost and Membrane Thickness.5.3.2 Module Maintenance and Operating Costs.5.3.3 Overview of Membrane Fabrication Methods.5.4 Membrane Module Design and Construction.5.4.1 Design of the Module Shell.5.4.2 Membrane Sealing Options.5.4.3 Commercial Applicability.6 The Evolution of Materials and Architecture for Oxygen Transport Membranes (John Sirman).6.1 Introduction.6.2 Oxygen Separation and Collection.6.2.1 Background for Selection of Materials for Oxygen Separation and Collection.6.2.2 Membrane Materials Concepts.6.2.3 Membrane Architecture Concepts.6.2.4 Summary of Oxygen Separation Materials and Architecture.6.3 Syngas Production and Combustion Applications.6.3.1 Background for Selection of Materials for Syngas Production and Combustion Applications.6.3.2 Membrane Materials Concepts.6.3.3 Membrane Architecture Concepts.6.3.4 Summary of Syngas and Combustion Applications Materials and Architecture.7 Membranes for Promoting Partial Oxidation Chemistries (Anthony F. Sammells, James H. White, and Richard Mackay).7.1 Introduction.7.2 On the Nature of Perovskite-related Metal Oxides for Achieving Mixed Oxygen Anion and Electron Conduction.7.2.1 Background.7.2.2 Early Work towards the Selection of Mixed Conductors.7.2.3 Requirements for Oxygen Anion and Electronic Conduction within Perovskites.7.2.4 Empirical Factors Relating to Oxygen Anion Transport in Perovskiterelated Membranes.7.2.5 Introducing Electronic Conductivity into a Perovskite-related Lattice.7.3 The Application of Oxygen Transport Membranes to Partial Oxidation Chemistries.7.3.1 Natural Gas Conversion to Synthesis Gas - General Considerations.7.3.2 Methane Partial Oxidation to Synthesis Gas in Membrane Reactors.7.3.3 Liquid Fuel Reforming.7.3.4 Coal/Biomass to Synthesis Gas.7.3.5 Oxygen Reduction Catalysis Requirements in Oxygen Transport Membranes.7.3.6 Methane to Ethylene.7.3.7 Catalysis Considerations for Promoting Methane Coupling Reactions.7.3.8 Catalyst Implementation on Dense Oxygen Transport Media for Oxidative Coupling.7.3.9 Alkane Dehydrogenation.7.3.10 Hydrogen Sulfide Partial Oxidation.7.3.11 Some Thoughts on the Potential Contribution of Membrane Technology towards Realizing a Hydrogen Economy.8 Syngas Membrane Engineering Design and Scale-Up Issues. Application of Ceramic Oxygen Conducting Membranes (Michael Carolan).8.1 Membrane Design and Engineering.8.2 Reactor Design and Engineering.8.3 Planar Membrane Reactors.8.4 Ceramic-to-Ceramic Seals.8.5 Ceramic-to-Metal Seals.8.6 Summary and Conclusions.9 Economics Associated with Implementation of Membrane Reactors (Alessandra Criscuoli).9.1 Introduction.9.2 Membrane Reactors.9.3 Factors Influencing the Economics.9.4 Dense Membrane Reactors for the Water-Gas Shift Reaction.9.5 Economic Feasibility of Water-Gas Shift Pd-based Membrane Reactors.9.6 Future Directions.Index.