FUNDAMENTALS OF INORGANIC MEMBRANE SCIENCE AND TECHNOLOGY

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1 Membrane Science and Technology Series, 4 FUNDAMENTALS OF INORGANIC MEMBRANE SCIENCE AND TECHNOLOGY Edited by A.J. Burggraaf Laboratory of Inorganic Materials Science, Faculty of Chemical Technology, University of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands and L. Cot Laboratory des Materiaux et Procedes Membranes, (UMR 9987 CNRS-ENSCM-4411), Ecole Nationale Superieure de Chimie 8 Rue de l'ecole de Chimie, Montpellier, France 1996 ELSEVIER Amsterdam Lausanne New York Oxford Shannon Tokyo

vii Contents Preface List of contributors v xvii Chapter 1. GENERAL OVERVIEW, TRENDS AND PROSPECTS A.J. Burggraaf and L. Cot 1.1 Introduction 1 1.2 Market Situation and Prospects 2 1.

2 vii Contents Preface List of contributors v xvii Chapter 1. GENERAL OVERVIEW, TRENDS AND PROSPECTS A.J. Burggraaf and L. Cot 1.1 Introduction Market Situation and Prospects Main Barriers to Technological Development and Acceptance Requirements and Issues Characteristics of ceramic fabrication State of the Art and Needs Availability and cost Reliability Long-term stability Surface area to volume ratio Specific combinations of high Separation factors and high permeation Trends, Technological and Scientific Prospects Infrastructure for Future Work Some Trends Prospects for Interesting Membrane Applications Industrial production processes Energy-related applications Environmental applications Others Interesting Fields for Future R&D Long-term chemical stability Thin-layer deposition technology Support technology Microporous membranes for gas/vapour Separation Nanofiltration membranes Dense (non-porous) membranes and surface reaction limitation Mixed (hybrid) processes and materials 19 References 19 Chapter 2. IMPORTANT CHARACTERISTICS OF INORGANIC MEMBRANES A.J. Burggraaf 2.1 Introduction Types of Inorganic Membranes 21

vm 2.3 Microstructural Pore and Pore Network Characteristics 23 2.3.1 Modified Structures 26 2.3.2 Supports 27 2.4 Architecture of Membrane Systems 27 2.5

3 vm 2.3 Microstructural Pore and Pore Network Characteristics Modified Structures Supports Architecture of Membrane Systems Some General Characteristics Commercially Available Inorganic Membranes Considerations on Chemical Resistance 33 References 34 Chapter 3. ADSORPTION PHENOMENA IN MEMBRANE SYSTEMS Yi Hua Ma 3.1 Introduction Adsorption Isotherms Types of Isotherms The Langmuir Isotherm The BET Isotherms Isotherms Derived from the Equation of State The Potential Theory Experimental Techniques Determination of Adsorption Isotherms Surface Area Determinations Pore Size Distribution Adsorption on Membranes Adsorption of Gases on Microporous Silica Membranes and Interrelation between Adsorption and Permeation Adsorption on Sol-Gel Derived Ceramic Membranes Liquid Adsorption on Membranes Summary 64 References 64 Chapter 4. METHODS FOR THE CHARACTERISATION OF POROUS STRUCTURE IN MEMBRANE MATERIALS A. Julbe and J.D.F. Ramsay 4.1 General Introduction Description of Porous Materials Definitions Origin of Pore Structure Quantitative Description of Pore Structures Models for Porous Structures Static Characterisation Techniques Stereology Intrusive Methods Mercury porosimetry Gas adsorption/desorption isotherms (physisorption) Calorimetric determinations Nuclear magnetic resonance Non-intrusive Methods 91

4.3.3.1 Radiation scattering 91 4.3.3.2 Wave propagation 94 4.3.3.3 Ion-beam analysis 96 4.3.3.4 Positron lifetime spectroscopy 97 4.4 Dynamic Characterisation Techniques 98 4.4.1 Rejection Measurements 98 4.

4 Radiation scattering Wave propagation Ion-beam analysis Positron lifetime spectroscopy Dynamic Characterisation Techniques Rejection Measurements Liquid Displacement Techniques Liquid/gas methods (bubble point, liquid expulsion permporometry) Liquid-liquid displacement porosimetry (or biliquid permporometry) Fluid Flow Measurements Liquid permeability Gas permeability Permporometry Conclusion and Recommendations 106 References 110 Chapter 5. CERAMIC PROCESSING TECHNIQUES OF SUPPORT SYSTEMS FOR MEMBRANES SYNTHESIS A. Larbot 5.1 Introduction Extrusion Ceramic Paste Preparation Tube Shaping, Drying and Firing An Example of Preparation Tape Casting Slurry Preparation Shaping and Fiat Ceramics Specific Characterization Methods for Supports Bubble Point Mechanical Resistance Burst pressure (test for tubes) Bending strength (test for cylindrical specimen) Conclusion 137 References 138 Chapter 6. PREPARATION OF ASYMMETRIC CERAMIC MEMBRANE SUPPORTS BY DIP-COATING B.C. Bonekamp 6.1 Introduction Supports for Ceramic Membranes The Multilayer Support System Support Requirements Layer Formation on Porous Substrates Suspensions and Sols 159 ix

X 6.2.4.1 Van der Waals attraction 163 6.2.4.2 Electrostatic interaction 164 6.2.4.3 Polymerie interaction 166 6.2.4.4 Rheology 171 6.2.5 Drying and Sintering of Particulate Coatings 175 6.2.6 Defects 178 6.

5 X Van der Waals attraction Electrostatic interaction Polymerie interaction Rheology Drying and Sintering of Particulate Coatings Defects Dip-coating with Porous Substrates Capillary Colloidal Filtration Continuum description Film-coating Coating flow dynamics Closer examination Substrate wetting and dewetting Stability of liquid coatings Macromolecular Thickeners and Binders Compact (Cake) Structure Applications Final Remarks 218 Acknowledgements 218 List of Symbols 219 References 221 Chapter 7. SOL-GEL CHEMISTRY AND ITS APPLICATION TO POROUS MEMBRANE PROCESSING Christian Guizard 7.1 Introduction Pore Formation in Sol-Gel Derived Ceramic Membranes Packing of Colloidal Particles Aggregation of Clusters Utilization of Template Agents Colloidal Suspensions to Prepare Mesoporous Membranes Chemistry of Colloidal Sols Examples of Membrane Preparation Inorganic Polymers to Prepare Microporous Membranes Formation and Aggregation of Clusters Examples of Membrane Preparation The Concept of Nanophase Ceramics Applied to the Preparation of Microporous Membranes Formation and Coating of Aqueous Nanoparticulate Sols Formation and Coating of Organic Nanoparticulate Sols Tailor-made Porous Membranes via Templates Containing Systems Utilization of Amphiphilic Media Insertion of Organic and Inorganic Entities or Polymer Particles in Gel Layers Conclusion 254 References 255

Chapter 8. FUNDAMENTALS OF MEMBRANE TOP-LAYER SYNTHESIS AND PROCESSING A.J. Burggraaf 8.1 Synthesis and Processing of Supported Mesoporous Membranes 259 8.1.1 Introduction 259 8.1.2 Film Formation 260 8.

6 Chapter 8. FUNDAMENTALS OF MEMBRANE TOP-LAYER SYNTHESIS AND PROCESSING A.J. Burggraaf 8.1 Synthesis and Processing of Supported Mesoporous Membranes Introduction Film Formation Initial layer formation Mesoporous film formation Theoretical aspects of the drying process from lyogel to xerogel film Consolidation to the final membrane structure by heating Illustrative Experimental Observations of Stress and Cracking in Membranes Stress measurements in supported porous membranes Drying characteristics of membranes Stress and cracking in membranes during drying Stress formation in membranes during calcination A model discussion of stress and avoiding cracking Thermal Stability of Ceramic Membranes Synthesis and Processing of Supported Microporous Membranes Microporous Membranes Obtained by Sol-Gel Processes Introduction and overview of film formation Important parameters in precursor synthesis Illustrative examples of membrane synthesis and microstructure development Microporous Membranes Obtained by CVD CVD methods Other methods and microporous membrane Systems Zeolite Membranes Overview and introduction to zeolite chemistry Illustrative examples of zeolite membrane synthesis and processing Conclusions and Evaluation 322 References 324 Chapter 9. TRANSPORT AND SEPARATION PROPERTIES OF MEMBRANES WITH GASES AND VAPOURS A.J. Burggraaf 9.1 Introduction Chapter Outline Overview of Important Points Gas Transport in Simple Membrane Structures Important Concepts Pore Characteristics and Membrane Architecture Single Gas Permeation in Macroporous and Mesoporous Systems Viscousflow 337 xi

xii 9.2.3.2 Knudsen diffusion and the transition region 338 9.2.3.3 Surface diffusion and capillary condensation 345 9.2.4 Permeation in binary gas mixtures in macroporous and mesoporous membranes 355 9.

7 xii Knudsen diffusion and the transition region Surface diffusion and capillary condensation Permeation in binary gas mixtures in macroporous and mesoporous membranes General considerations Knudsen diffusion Viscous Flow and the Transition Region Separation of Binary Mixtures in Simple Mesoporous Membranes Important Concepts Separation in the Knudsen and Transition Regions Separation with Surface Diffusion and Capillary Condensation Permeation and Separation in Microporous Membranes Introduction and Important Concepts Phenomenological Description of Single Gas Permeation Qualitative description of gas permeation Quantitative description of gas permeation and Separation Permeation and Separation in binary (ternary) gas mixtures Illustrative examples of permeation and Separation with microporous membranes Surface Effects on Permeation in Microporous Membranes Permeation and Separation in More Complicated Systems HollowFibres Multilayered, Asymmetrie Supported Systems Overview of Important Results Introductory Remarks Typical Permeation and Separation Data for Porous Membranes Comparison of Permeation and Separation Data of Porous and Dense Membranes Conclusions and Evaluation 424 List of Symbols 425 References 427 Chapter 10. DENSE CERAMIC MEMBRANES FOR OXYGEN SEPARATION H.J.M. Bouwmeester and A.J. Burggraaf 10.1 Introduction General Survey Major Membrane Concepts Data: Oxygen Permeability of Solid Oxide Membranes Factors Controlling Oxygen Permeation Fundamentals Bulk Transport Wagner equation Chemical diffusion coefficient 451

10.3.1.3 Trapping of electronic and ionic defects 453 10.3.1.4 Empirical equations 454 10.3.2 Surface Oxygen Exchange 455 10.3.2.1 Characteristic membrane thickness L c 456 10.3.2.2 MeasuringL c 459 10.

8 Trapping of electronic and ionic defects Empirical equations Surface Oxygen Exchange Characteristic membrane thickness L c MeasuringL c The effect of surface roughness and porosity Solid Oxide Electrolytes Introduction Diffusion of electronic Charge carriers Oxygen Semi-permeability of Oxide Electrolytes Modelling equations Examples Electrochemical Oxygen Separation Oxygen pump Dual-phase composites Introducing Electronic Conduction in Fluorite-type Oxygen Ion Conductors Introduction Defect Chemistry Examples Accceptor-doped Perovskite and Perovskite-related Oxides Introduction Structure and Defect Chemistry Perovskite Structure Nonstoichiomerry Localized versus Delocalized Elections Oxygen Desorption and Perovskite Stability Equations for Oxygen Transport Electronic Conductivity Extended Defects and Vacancy Ordering Static Lattice Simulation Vacancy Ordering Microdomain Formation Brownmillerite Structure High Temperature NMR Observations from Permeability Measurements SrCoo.8Feo ^ Experimental difficulties Surface exchange kinetics Behaviour in large Po 2 -gradients Grain boundary diffusivity Final Remarks 510 Acknowledgements 513 List of Abbreviations and Symbols 513 References 515

XIV Chapter 11. CURRENT DEVELOPMENTS AND FUTURE RESEARCH IN CATALYTIC MEMBRANE REACTORS Jose Sanchez and Theodore T. Tsotsis 11.1 Introduction 529 11.2 Dense Metal Membrane Reactors 532 11.2.1 Cost and Availability 534 11.

9 XIV Chapter 11. CURRENT DEVELOPMENTS AND FUTURE RESEARCH IN CATALYTIC MEMBRANE REACTORS Jose Sanchez and Theodore T. Tsotsis 11.1 Introduction Dense Metal Membrane Reactors Cost and Availability Mechanical and Thermal Stability Poisoning and Carbon Deposition Problems Porous Inorganic Membrane Reactors Solid Oxide Membranes Theoretical Considerations Emerging Applications Concluding Remarks 560 Acknowledgements 561 References 561 Chapter 12. TRANSPORT AND FOULING PHENOMENA IN LIQUID PHASE SEPARATION WITH INORGANIC AND HYBRID MEMBRANES Christian Guizard and Gilbert Rios 12.1 Introduction Basic Phenomena in Pressure Driven Processes Modelling of Hydrodynamics and Mass Transport Fouling Specific Aspects Attached to Ceramic Membranes Recent Developments in Microfiltration and Ultrafiltration with Ceramic Membranes Hydrodynamics of Micro- and Ultrafiltration Systems Influence of Membrane Material on Permeability and Solute Rejection Nanofiltration with Ceramic Membranes Separation of Neutral Solutes in Absence of Electrolytes Salt Rejection of Electrolyte Solutions Separation of Aqueous Ionized Molecule-Salt Solutions Prospective Aspects Organic-Inorganic Hybrid Membranes and Related Processes Coupled Membrane Processes Conclusion 613 References 614 Chapter 13. APPLICATIONS OF CERAMIC MEMBRANES IN LIQUID FILTRATION C.A.M. Siskens 13.1 Introduction Treatment of Wastes Wastes of Oily Emulsions Compressor-condensate Centralised treatment of industrial emulsions 621

XV 13.2.1.3 Bilge water treatment 621 13.2.1.4 Vegetable waste water 622 13.2.2 Wastes Based on Semi-solids 622 13.2.2.1 Fish factory effluent 622 13.2.2.2 Manure 623 13.3 Regeneration 623 13.3.1 Recycling of Solids from Suspensions 623 13.

10 XV Bilge water treatment Vegetable waste water Wastes Based on Semi-solids Fish factory effluent Manure Regeneration Recycling of Solids from Suspensions Ceramics industry Paintandink Lifetime Extension of Cleaning Baths Alkaline degreasing baths Industrial washing Operations Recycling in Chemical Processes Cleaning of organic and inorganic reagents Galvanic baths Processing Treatment of Liquid Products Fruit Juices Beerbrewing Beer and wine clarification Potable water Treatment of Semi-solid Products Proteins Whey Sugars Paper and pulp Biotechnology 632 Acknowledgements 634 References 634 Chapter 14. FEASIBILITY OF THE APPLICATION OF POROUS INORGANIC GAS SEPARATION MEMBRANES IN SOME LARGE-SCALE CHEMICAL PROCESSES Henk M. van Veen, Maarten Bracht, Edwin Hamoen and Peter T. Alderliesten 14.1 Introduction Background Information Materials Membrane Reactors Membrane Process Modelling Gas Separation Applications for Inorganic Membranes Dehydrogenation of Propane Introduction Thermodynamics of propane dehydrogenation Adiabatic reactor concepts; reactor modelling evaluation Isothermal reactor concepts; economic evaluation General conclusions propane dehydrogenation 657

xvi 14.3.2 Dehydrogenation of Ethylbenzene to Styrene 657 14.3.2.1 Introduction 657 14.3.2.2 Conventional process description 658 14.3.2.3 Implementation of membranes 659 14.3.2.4 Results 661 14.3.2.5 Discussion 664 14.

11 xvi Dehydrogenation of Ethylbenzene to Styrene Introduction Conventional process description Implementation of membranes Results Discussion Conclusions Water-Gas Shift Membrane Reactor Introduction WGS membrane reactor for CO2 emission control Full-scale process considerations Conclusion Conclusions 673 Acknowledgements 674 List of Symbols and Abbreviations 675 Appendix 676 References 676 Subject Index 681

Basic Principles of Membrane Technolog

Basic Principles of Membrane Technolog by Marcel Mulder Center for Membrane Science and Technology, University oftwente, Enschede, The Netherlands ff KLUWER ACADEMIC PUBLISHERS DORDRECHT / BOSTON / LONDON