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Adsorption promises to play an integral role in several future energy and environmental technologies, including hydrogen storage, CO removal for fuel cell technology, desulfurization of transportation fuels, and technologies for meeting higher standards on air and water pollutants. Ralph Yang's Adsorbents provides a single and comprehensive source of knowledge for all commercial and new sorbent materials, presenting the fundamental principles for their syntheses, their adsorption properties, and their present and potential applications for separation and purification. Chapter topics in this…mehr
Adsorption promises to play an integral role in several future energy and environmental technologies, including hydrogen storage, CO removal for fuel cell technology, desulfurization of transportation fuels, and technologies for meeting higher standards on air and water pollutants. Ralph Yang's Adsorbents provides a single and comprehensive source of knowledge for all commercial and new sorbent materials, presenting the fundamental principles for their syntheses, their adsorption properties, and their present and potential applications for separation and purification. Chapter topics in this authoritative, forward-looking volume include: - Formulas for calculating the basic forces or potentials for adsorption - Calculation of pore-size distribution from a single adsorption isotherm - Rules for sorbent selection - Fundamental principles for syntheses/preparation, adsorption properties, and applications of commercially available sorbents - Mesoporous molecular sieves and zeolites -¿-complexation sorbents and their applications - Carbon nanotubes, pillared clays, and polymeric resins Yang covers the explosion in the development of new nanoporous materials thoroughly, as the adsorption properties of some of these materials have remained largely unexplored. The whole of this book benefits from the new adsorbent designs made possible by the increase in desktop computing and molecular simulation, making Adsorbents useful to both practicing laboratories and graduate programs. Ralph Yang's comprehensive study contributes significantly to the resolution of separation and purification problems by adsorption technologies.
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RALPH T. YANG, PhD, is Dwight F. Benton Professor of Chemical Engineering at the University of Michigan.
Inhaltsangabe
Preface xi 1 Introductory Remarks 1 1.1. Equilibrium Separation and Kinetic Separation 2 1.2. Commercial Sorbents and Applications 3 1.3. New Sorbents and Future Applications 6 References 7 2 Fundamental Factors for Designing Adsorbent 8 2.1. Potential Energies for Adsorption 8 2.2. Heat of Adsorption 10 2.3. Effects of Adsorbate Properties on Adsorption: Polarizability ( ), Dipole Moment ( ), and Quadrupole Moment (Q) 11 2.4. Basic Considerations for Sorbent Design 12 2.4.1. Polarizability ( ), Electronic Charge (q), and van der Waals Radius (r) 12 2.4.2. Pore Size and Geometry 13 References 16 3 Sorbent Selection: Equilibrium Isotherms, Diffusion, Cyclic Processes, and Sorbent Selection Criteria 17 3.1. Equilibrium Isotherms and Diffusion 18 3.1.1. Langmuir Isotherms for Single and Mixed Gases 18 3.1.2. Potential Theory Isotherms for Single and Mixed Gases 20 3.1.3. Ideal Adsorbed Solution Theory for Mixture and Similarities with Langmuir and Potential Theories 22 3.1.4. Diffusion in Micropores: Concentration Dependence and Predicting Mixed Diffusivities 23 3.2. Temperature Swing Adsorption and Pressure Swing Adsorption 27 3.2.1. Temperature Swing Adsorption 28 3.2.2. Pressure Swing Adsorption 30 3.3. Simple Criteria for Sorbent Selection 40 References 49 4 Pore Size Distribution 54 4.1. The Kelvin Equation 54 4.2. Horv ath-Kawazoe Approach 55 4.2.1. The Original HK Slit-Shaped Pore Model 57 4.2.2. Modified HK Model for Slit-Shaped Pores 60 4.2.3. Modified Model for Cylindrical Pores 68 4.3. The Integral Equation Approach 74 References 76 5 Activated Carbon 79 5.1. Formation and Manufacture of Activated Carbon 79 5.2. Pore Structure and Standard Tests for Activated Carbon 82 5.3. General Adsorption Properties 84 5.4. Surface Chemistry and Its Effects on Adsorption 86 5.4.1. Effects of Surface Functionalities on Gas Adsorption 89 5.5. Adsorption from Solution and Effects of Surface Functionalities 92 5.5.1. Adsorption from Dilute Solution (Particularly Phenols) 93 5.5.2. Effects of Surface Functionalities on Adsorption 99 5.6. Activated Carbon Fibers 104 5.6.1. Adsorption Isotherms 109 5.7. Carbon Molecular Sieves 109 5.7.1. Carbon Deposition Step 114 5.7.2. Kinetic Separation: Isotherms and Diffusivities 115 5.7.3. Carbon Molecular Sieve Membranes 117 References 123 6 Silica Gel, MCM, and Activated Alumina 131 6.1. Silica Gels: Preparation and General Properties 131 6.2. Surface Chemistry of Silicas: The Silanol Groups 134 6.3. The Silanol Number (OHnm 1) 135 6.4. MCM-41 139 6.5. Chemical Modification of Silicas and Molecular Imprinting 141 6.6. Activated Alumina 146 6.7. Activated Alumina as Special Sorbents 150 References 154 7 Zeolites and Molecular Sieves 157 7.1. Zeolite Types A, X, and Y 158 7.1.1. Structure and Cation Sites of Type A Zeolite 158 7.1.2. Structure and Cation Sites of Types X and Y Zeolites 160 7.1.3. Examples of Molecular Sieving 161 7.2. Zeolites and Molecular Sieves: Synthesis and Molecular Sieving Properties 164 7.2.1. Synthesis of Zeolites A, X, and Y 164 7.2.2. Organic Additives (Templates) in Synthesis of Zeolites and Molecular Sieves 165 7.3. Unique Adsorption Properties: Anionic Oxygens and Isolated Cations 173 7.4. Interactions of Adsorbate with Cations: Effects of Cation Site, Charge, and Ionic Radius 175 7.4.1. Cation Sites 175 7.4.2. Effects of Cation Sites on Adsorption 180 7.4.3. Effects of Cation Charge and Ionic Radius 183 References 187 8 -Complexation Sorbents and Applications 191 8.1. Preparation of Three Types of Sorbents 192 8.1.1. Supported Monolayer Salts 193 8.1.2. Ion-Exchanged Zeolites 197 8.1.3. Ion-Exchanged Resins 201 8.2. Molecular Orbital Theory Calculations 202 8.2.1. Molecular Orbital Theory-Electronic Structure Methods 202 8.2.2. Semi-Empirical Methods 203 8.2.3. Density Functional Theory Methods 203 8.2.4. Ab Initio Methods 204 8.2.5. Basis Set 205 8.2.6. Effective Core Potentials 205 8.2.7. Model Chemistry and Molecular Systems 206 8.2.8. Natural Bond Orbital 207 8.2.9. Adsorption Bond Energy Calculation 208 8.3. Nature of -Complexation Bonding 208 8.3.1. Understanding -Complexation Bond through Molecular Orbital Theory 209 8.3.2. -Complexation Bonds with Different Cations 212 8.3.3. Effects of Different Anions and Substrates 213 8.4. Bulk Separations by -Complexation 216 8.4.1. Deactivation of -Complexation Sorbents 216 8.4.2. CO Separation by -Complexation 216 8.4.3. OlefinParaffin Separations 219 8.4.4. AromaticsAliphatics Separation 220 8.4.5. Possible Sorbents for Simulated Moving-Bed Applications 222 8.5. Purification by -Complexation 223 8.5.1. Removal of Dienes from Olefins 224 8.5.2. Removal of Aromatics from Aliphatics 226 References 227 9 Carbon Nanotubes, Pillared Clays, and Polymeric Resins 231 9.1. Carbon Nanotubes 231 9.1.1. Catalytic Decomposition 233 9.1.2. Arc Discharge and Laser Vaporization 241 9.1.3. Adsorption Properties of Carbon Nanotubes 243 9.2. Pillared Clays 253 9.2.1. Syntheses of PILCs 253 9.2.2. Micropore Size Distribution 256 9.2.3. Cation Exchange Capacity 258 9.2.4. Adsorption Properties 260 9.2.5. PILC and Acid-Treated Clay as Supports 262 9.3. Polymeric Resins 264 9.3.1. Pore Structure, Surface Properties, and Applications 266 9.3.2. Comparisons of Resins and Activated Carbon 269 9.3.3. Mechanism of Sorption and Gas-Phase Applications 271 References 273 10 Sorbents for Applications 280 10.1. Air Separation 280 10.1.1. 5A and 13X Zeolites 282 10.1.2. Li-LSX Zeolite 283 10.1.3. Type X Zeolite with Alkaline Earth Ions 288 10.1.4. LSX Zeolite Containing Ag (AgLiLSX) 289 10.1.5. Oxygen-Selective Sorbents 296 10.2. Hydrogen Purification 303 10.3. Hydrogen Storage 305 10.3.1. Metal Hydrides 306 10.3.2. Carbon Nanotubes 308 10.4. Methane Storage 321 10.5. OlefinParaffin Separations 326 10.5.1. Sorbents 326 10.5.2. PSA Separations 328 10.5.3. Other Sorbents 334 10.6. NitrogenMethane Separation 334 10.6.1. Clinoptilolites 336 10.6.2. ETS-4 341 10.6.3. PSA Simulation: Comparison of Sorbents 344 10.7. Desulfurization of Transportation Fuels 344 10.7.1. Fuel and Sulfur Compositions 347 10.7.2. Sorbents Studied or Used 349 10.7.3. -Complexation Sorbent 350 10.8. Removal of Aromatics from Fuels 361 10.9. NOx Removal 363 References 371 Author Index 383 Subject Index 403
Preface xi 1 Introductory Remarks 1 1.1. Equilibrium Separation and Kinetic Separation 2 1.2. Commercial Sorbents and Applications 3 1.3. New Sorbents and Future Applications 6 References 7 2 Fundamental Factors for Designing Adsorbent 8 2.1. Potential Energies for Adsorption 8 2.2. Heat of Adsorption 10 2.3. Effects of Adsorbate Properties on Adsorption: Polarizability ( ), Dipole Moment ( ), and Quadrupole Moment (Q) 11 2.4. Basic Considerations for Sorbent Design 12 2.4.1. Polarizability ( ), Electronic Charge (q), and van der Waals Radius (r) 12 2.4.2. Pore Size and Geometry 13 References 16 3 Sorbent Selection: Equilibrium Isotherms, Diffusion, Cyclic Processes, and Sorbent Selection Criteria 17 3.1. Equilibrium Isotherms and Diffusion 18 3.1.1. Langmuir Isotherms for Single and Mixed Gases 18 3.1.2. Potential Theory Isotherms for Single and Mixed Gases 20 3.1.3. Ideal Adsorbed Solution Theory for Mixture and Similarities with Langmuir and Potential Theories 22 3.1.4. Diffusion in Micropores: Concentration Dependence and Predicting Mixed Diffusivities 23 3.2. Temperature Swing Adsorption and Pressure Swing Adsorption 27 3.2.1. Temperature Swing Adsorption 28 3.2.2. Pressure Swing Adsorption 30 3.3. Simple Criteria for Sorbent Selection 40 References 49 4 Pore Size Distribution 54 4.1. The Kelvin Equation 54 4.2. Horv ath-Kawazoe Approach 55 4.2.1. The Original HK Slit-Shaped Pore Model 57 4.2.2. Modified HK Model for Slit-Shaped Pores 60 4.2.3. Modified Model for Cylindrical Pores 68 4.3. The Integral Equation Approach 74 References 76 5 Activated Carbon 79 5.1. Formation and Manufacture of Activated Carbon 79 5.2. Pore Structure and Standard Tests for Activated Carbon 82 5.3. General Adsorption Properties 84 5.4. Surface Chemistry and Its Effects on Adsorption 86 5.4.1. Effects of Surface Functionalities on Gas Adsorption 89 5.5. Adsorption from Solution and Effects of Surface Functionalities 92 5.5.1. Adsorption from Dilute Solution (Particularly Phenols) 93 5.5.2. Effects of Surface Functionalities on Adsorption 99 5.6. Activated Carbon Fibers 104 5.6.1. Adsorption Isotherms 109 5.7. Carbon Molecular Sieves 109 5.7.1. Carbon Deposition Step 114 5.7.2. Kinetic Separation: Isotherms and Diffusivities 115 5.7.3. Carbon Molecular Sieve Membranes 117 References 123 6 Silica Gel, MCM, and Activated Alumina 131 6.1. Silica Gels: Preparation and General Properties 131 6.2. Surface Chemistry of Silicas: The Silanol Groups 134 6.3. The Silanol Number (OHnm 1) 135 6.4. MCM-41 139 6.5. Chemical Modification of Silicas and Molecular Imprinting 141 6.6. Activated Alumina 146 6.7. Activated Alumina as Special Sorbents 150 References 154 7 Zeolites and Molecular Sieves 157 7.1. Zeolite Types A, X, and Y 158 7.1.1. Structure and Cation Sites of Type A Zeolite 158 7.1.2. Structure and Cation Sites of Types X and Y Zeolites 160 7.1.3. Examples of Molecular Sieving 161 7.2. Zeolites and Molecular Sieves: Synthesis and Molecular Sieving Properties 164 7.2.1. Synthesis of Zeolites A, X, and Y 164 7.2.2. Organic Additives (Templates) in Synthesis of Zeolites and Molecular Sieves 165 7.3. Unique Adsorption Properties: Anionic Oxygens and Isolated Cations 173 7.4. Interactions of Adsorbate with Cations: Effects of Cation Site, Charge, and Ionic Radius 175 7.4.1. Cation Sites 175 7.4.2. Effects of Cation Sites on Adsorption 180 7.4.3. Effects of Cation Charge and Ionic Radius 183 References 187 8 -Complexation Sorbents and Applications 191 8.1. Preparation of Three Types of Sorbents 192 8.1.1. Supported Monolayer Salts 193 8.1.2. Ion-Exchanged Zeolites 197 8.1.3. Ion-Exchanged Resins 201 8.2. Molecular Orbital Theory Calculations 202 8.2.1. Molecular Orbital Theory-Electronic Structure Methods 202 8.2.2. Semi-Empirical Methods 203 8.2.3. Density Functional Theory Methods 203 8.2.4. Ab Initio Methods 204 8.2.5. Basis Set 205 8.2.6. Effective Core Potentials 205 8.2.7. Model Chemistry and Molecular Systems 206 8.2.8. Natural Bond Orbital 207 8.2.9. Adsorption Bond Energy Calculation 208 8.3. Nature of -Complexation Bonding 208 8.3.1. Understanding -Complexation Bond through Molecular Orbital Theory 209 8.3.2. -Complexation Bonds with Different Cations 212 8.3.3. Effects of Different Anions and Substrates 213 8.4. Bulk Separations by -Complexation 216 8.4.1. Deactivation of -Complexation Sorbents 216 8.4.2. CO Separation by -Complexation 216 8.4.3. OlefinParaffin Separations 219 8.4.4. AromaticsAliphatics Separation 220 8.4.5. Possible Sorbents for Simulated Moving-Bed Applications 222 8.5. Purification by -Complexation 223 8.5.1. Removal of Dienes from Olefins 224 8.5.2. Removal of Aromatics from Aliphatics 226 References 227 9 Carbon Nanotubes, Pillared Clays, and Polymeric Resins 231 9.1. Carbon Nanotubes 231 9.1.1. Catalytic Decomposition 233 9.1.2. Arc Discharge and Laser Vaporization 241 9.1.3. Adsorption Properties of Carbon Nanotubes 243 9.2. Pillared Clays 253 9.2.1. Syntheses of PILCs 253 9.2.2. Micropore Size Distribution 256 9.2.3. Cation Exchange Capacity 258 9.2.4. Adsorption Properties 260 9.2.5. PILC and Acid-Treated Clay as Supports 262 9.3. Polymeric Resins 264 9.3.1. Pore Structure, Surface Properties, and Applications 266 9.3.2. Comparisons of Resins and Activated Carbon 269 9.3.3. Mechanism of Sorption and Gas-Phase Applications 271 References 273 10 Sorbents for Applications 280 10.1. Air Separation 280 10.1.1. 5A and 13X Zeolites 282 10.1.2. Li-LSX Zeolite 283 10.1.3. Type X Zeolite with Alkaline Earth Ions 288 10.1.4. LSX Zeolite Containing Ag (AgLiLSX) 289 10.1.5. Oxygen-Selective Sorbents 296 10.2. Hydrogen Purification 303 10.3. Hydrogen Storage 305 10.3.1. Metal Hydrides 306 10.3.2. Carbon Nanotubes 308 10.4. Methane Storage 321 10.5. OlefinParaffin Separations 326 10.5.1. Sorbents 326 10.5.2. PSA Separations 328 10.5.3. Other Sorbents 334 10.6. NitrogenMethane Separation 334 10.6.1. Clinoptilolites 336 10.6.2. ETS-4 341 10.6.3. PSA Simulation: Comparison of Sorbents 344 10.7. Desulfurization of Transportation Fuels 344 10.7.1. Fuel and Sulfur Compositions 347 10.7.2. Sorbents Studied or Used 349 10.7.3. -Complexation Sorbent 350 10.8. Removal of Aromatics from Fuels 361 10.9. NOx Removal 363 References 371 Author Index 383 Subject Index 403
Rezensionen
"...fulfils existing demand for a simple and comprehensive text devoted to commercial and novel adsorbents...a valuable guide..." Journal of the American Chemical Society, Vol. 125, No. 39, 2003
"...a very good book on a very important topic. Well-written, resplendent with figures and tables, and well-referenced are some of my observations." (Journal of Hazardous Materials, 109, 2004) "...fulfils existing demand for a simple and comprehensive text devoted to commercial and novel adsorbents...a valuable guide..." (Journal of the American Chemical Society, Vol. 125, No. 39, 2003)
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