m WILEY- ADSORBENTS: FUNDAMENTALS AND APPLICATIONS Ralph T. Yang Dwight F. Benton Professor of Chemical Engineering University of Michigan
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1 ADSORBENTS: FUNDAMENTALS AND APPLICATIONS Ralph T. Yang Dwight F. Benton Professor of Chemical Engineering University of Michigan m WILEY- INTERSCIENCE A JOHN WILEY & SONS, INC., PUBLICATION
2 Preface xi 1 Introductory Remarks 1.1. Equilibrium Separation and Kinetic Separation / Commercial Sorbents and Applications / New Sorbents and Future Applications / 6 References / 7 2 Fundamental Factors for Designing Adsorbent Potential Energies for Adsorption / Heat of Adsorption / Effects of Adsorbate Properties on Adsorption: Polanzability (a), Dipole Moment (/x), and Quadrupole Moment (Q) / Basic Considerations for Sorbent Design / Polanzability (a), Electronic Charge (q), and van der Waals Radius (r) / Pore Size and Geometry / 13 References / 16 3 Sorbent Selection: Equilibrium Isotherms, Diffusion, Cyclic 17 Processes, and Sorbent Selection Criteria 3.1. Equilibrium Isotherms and Diffusion / Langmuir Isotherms for Single and Mixed Gases / Potential Theory Isotherms for Single and Mixed Gases / Ideal Adsorbed Solution Theory for Mixture and Similarities with Langmuir and Potential Theories / 22 v
3 Diffusion in Micropores: Concentration Dependence and Predicting Mixed Diffusivities / Temperature Swing Adsorption and Pressure Swing Adsorption / Temperature Swing Adsorption / Pressure Swing Adsorption / Simple Criteria for Sorbent Selection / 40 References / 49 Pore Size Distribution 4.1. The Kelvin Equation / Horväth-Kawazoe Approach / The Original HK Slit-Shaped Pore Model / Modified HK Model for Slit-Shaped Pores / Modified Model for Cylindrical Pores / The Integral Equation Approach / 74 References / 76 Activated Carbon 5.1. Formation and Manufacture of Activated Carbon / Pore Structure and Standard Tests for Activated Carbon / General Adsorption Properties / Surface Chemistry and Its Effects on Adsorption / Effects of Surface Functionalities on Gas Adsorption / Adsorption from Solution and Effects of Surface Functionalities / Adsorption from Dilute Solution (Particularly Phenols) / Effects of Surface Functionalities on Adsorption / Activated Carbon Fibers / Adsorption Isotherms / Carbon Molecular Sieves / Carbon Deposition Step / Kinetic Separation: Isotherms and Diffusivities / Carbon Molecular Sieve Membranes / 117 References / 123
4 Silica Gel, MCM, and Activated Alumina 6.1. Silica Gels: Preparation and General Properties / 6.2. Surface Chemistry of Silicas: The Silanol Groups 6.3. The Silanol Number (OH/nm" 1 ) / MCM-41 / Chemical Modification of Silicas and Molecular Imprinting / Activated Alumina / Activated Alumina as Special Sorbents / 150 References / / 134 Zeolites and Molecular Sieves 7.1. Zeolite Types A, X, and Y / Structure and Cation Sites of Type A Zeolite / Structure and Cation Sites of Types X and Y Zeolites / Examples of Molecular Sieving / Zeolites and Molecular Sieves: Synthesis and Molecular Sieving Properties / Synthesis of Zeolites A, X, and Y / Organic Additives (Templates) in Synthesis of Zeolites and Molecular Sieves / Unique Adsorption Properties: Anionic Oxygens and Isolated Cations / Interactions of Adsorbate with Cations: Effects of Cation Site, Charge, and Ionic Radius / Cation Sites / Effects of Cation Sites on Adsorption / Effects of Cation Charge and Ionic Radius / 183 References / 187 jr-complexation Sorbents and Applications 8.1. Preparation of Three Types of Sorbents / Supported Monolayer Salts / Ion-Exchanged Zeolites / Ion-Exchanged Resins / Molecular Orbital Theory Calculations / Molecular Orbital Theory Electronic Structure Methods / Semi-Empirical Methods / 203
5 Density Functional Theory Methods / Ab Initio Methods / Basis Set / Effective Core Potentials / Model Chemistry and Molecular Systems / Natural Bond Orbital / Adsorption Bond Energy Calculation / Nature of 7T-Complexation Bonding / Understanding 7r-Complexation Bond through Molecular Orbital Theory / r-Complexation Bonds with Different Cations / Effects of Different Anions and Substrates / Bulk Separations by 7r-Complexation / Deactivation of 7r-Complexation Sorbents / CO Separation by 7r-Complexation / Olefin/Paraffin Separations / Aromatics/Aliphatics Separation / Possible Sorbents for Simulated Moving-Bed Applications / Purification by 7r-Complexation / Removal of Dienes from Olefins / Removal of Aromatics from Aliphatics / 226 References / 227 Carbon Nanotubes, Pillared Clays, and Polymerie Resins Carbon Nanotubes / Catalytic Decomposition / Are Discharge and Laser Vaporization / Adsorption Properties of Carbon Nanotubes / Pillared Clays / Syntheses of PILCs / Micropore Size Distribution / Cation Exchange Capacity / Adsorption Properties / PILC and Acid-Treated Clay as Supports / Polymerie Resins / Pore Structure, Surface Properties, and Applications / 266
6 JX Comparisons of Resins and Activated Carbon / Mechanism of Sorption and Gas-Phase Applications / 271 References / Sorbents for Applications Air Separation / A and 13X Zeolites / Li-LSX Zeolite / Type X Zeolite with Alkaline Earth Ions / LSX Zeolite Containing Ag (AgLiLSX) / Oxygen-Selective Sorbents / Hydrogen Purification / Hydrogen Storage / Metal Hydrides / Carbon Nanotubes / Methane Storage / Olefin/Paraffin Separations / Sorbents / PSA Separations / Other Sorbents / Nitrogen/Methane Separation / Clinoptilolites / ETS-4 / PSA Simulation: Comparison of Sorbents / Desulfurization of Transportation Fuels / Fuel and Sulfur Compositions / Sorbents Studied or Used / r-Complexation Sorbents / Removal of Aromatics from Fuels / NO x Removal / 363 References / 371 Author Index 383 Subject Index 403
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