Aqueous phase adsorption : theory, simulations, and experiments

This book covers theoretical aspects of adsorption, followed by an introduction to molecular simulations and other numerical techniques that have become extremely useful as an engineering tool in recent times to understand the interplay of different mechanistic steps of adsorption. Further, the book provides brief experimental methodologies to use, test, and evaluate different types of adsorbents for water pollutants. Through different chapters contributed by accomplished researchers working in the broad area of adsorption, this book provides the necessary fundamental background required for an academician, industrial scientist or engineer to initiate studies in this area. Key Features Explores fundamentals of adsorption-based separation Provides physical insight into aqueous phase adsorption Includes theory, molecular and mesoscopic level simulation techniques and experiments Describes molecular simulations and lattice-Boltzmann method based models for aqueous phase adsorption Presents state-of-art experimental works particularly addressing removal of "emerging pollutants" from aqueous phase Cover 1 Half Title 2 Title Page 4 Copyright Page 5 Table of Contents 6 Preface 8 Editors 12 Contributors 14 Chapter 1: Theory, Molecular, Mesoscopic Simulations, and Experimental Techniques of Aqueous Phase Adsorption 16 1.1 Adsorption from Liquid Solution 17 1.2 Thermodynamics of Surface Adsorption 17 1.2.1 Langmuir Isotherm 18 1.2.2 Freundlich Isotherm 19 1.2.3 BET (Brunauer, Emmett and Teller) Isotherm 20 1.3 Computer Simulations for Adsorption Studies 20 1.3.1 Molecular Simulations 21 1.3.2 Monte Carlo Simulations 22 1.3.3 Molecular Dynamics (MD) Simulation 23 1.3.4 Average Properties 24 1.3.5 Density Profiles 24 1.3.6 Hydrogen Bonding 25 1.3.7 Diffusion Coefficient 26 1.3.7.1 Einstein Relation 27 1.3.7.2 Green-Kubo Relation 27 1.3.8 Residence Time 27 1.3.9 Free Energy Calculations 28 1.3.9.1 Basic Formulation of Free Energy Calculations 28 1.3.9.2 Umbrella Sampling Method 29 1.3.9.3 Weighted Histogram Analysis Method (WHAM) 31 1.4 Mesoscopic Approach 33 1.4.1 Introduction to LBM 35 1.4.2 D2Q9 Square Lattice 35 1.4.3 Model Development for the 2-D Flow of a Pure Fluid 36 1.4.4 Equilibrium Distribution Function 37 1.4.5 Boundary Conditions 39 1.4.6 LBM-Based Model for Adsorption in Packed Beds 44 1.4.7 Adsorption Breakthrough Analysis 45 1.4.8 Boundary Conditions 47 1.5 Experimental Techniques 47 1.5.1 Equilibrium Adsorption Loading from Flow Study 51 References 54 Chapter 2: Graphene Nanopores-Based Separation of Impurities from Aqueous Medium 58 2.1 Introduction 58 2.2 Separation of Metal Ions from Aqueous Solution 60 2.2.1 Graphene-Based Membranes 60 2.2.2 Graphene Oxide 64 2.3 Separation of Organic Compounds 69 2.4 Potential of Mean Force (PMF) 72 2.5 Summary 76 Acknowledgments 76 References 77 Chapter 3: Computational Chemistry Assisted Simulation for Metal Ion Separation in the Aqueous-Organic Biphasic Systems 84 3.1 Introduction 85 3.2 Complexation of U(VI) towards N,N-Dihexyl-2-ethylhexanamide (DH2EHA) 87 3.2.1 Structure and Structural Parameters of Various Chemical Species 88 3.2.2 Binding and Free Energy of Complexation 89 3.3 Complexation of  and Pu4+ towards N, N-dihexyloctanamide (DHOA) 91 3.3.1 Structure and Structural Parameters of Various Chemical Species 93 3.3.2 Free Energy of Extraction 95 3.4 Complexation Selectivity of  and Pu4+ Ion towards Tetramethyl Diglycolamide (TMDGA) 96 3.4.1 Structure and Structural Parameters of Various Chemical Species 97 3.4.2 Solvation and Free Energy of Extraction 100 3.5 Binding of  and Pu4+ Ions with Ethylene Glycol Methacrylate Phosphate Anchored Graphene Oxide 104 3.5.1 Structure and Thermodynamics 105 3.6 Uranyl-TBP Complexes at the Aqueous-Organic Interface 106 3.6.1 Structural Parameters 107 3.7 Separation of Minor Actinides using N-Donor Containing Extractants 111 3.8 Conclusion 113 Acknowledgments 114 References 114 Chapter 4: Aqueous Separation in Metal-Organic Frameworks: From Experiments to Simulations 126 4.1 Introduction 126 4.2 Water Stability 127 4.3 Experimental Studies 129 4.3.1 Cations 129 4.3.2 Anions 132 4.3.3 Organics 134 4.4 Simulation Studies 136 4.4.1 Water Desalination 137 4.4.2 Biofuel Purification 138 4.4.3 Aqueous Mixtures 139 4.5 Summary 141 Acknowledgments 142 References 142 Chapter 5: Coating of Nanoparticles in Aqueous Solutions: Insights from Molecular Dynamics Simulations 150 5.1 Introduction 150 5.2 Setting Up and Representation of Hybrid NPs in Water for Molecular Simulations 152 5.3 Gold Hybrid Nanoparticles 154 5.4 Silica Hybrid Nanoparticles 167 5.5 Conclusions 169 Acknowledgments 170 References 170 Chapter 6: Lattice-Boltzmann Modeling of Adsorption Breakthrough in Packed Beds 174 6.1 Introduction 174 6.2 Boundary Fitting Approach for Curvilinear Surface 175 6.3 Macroscopic Conservation Equations 181 6.4 Mesoscopic Lattice Boltzmann Equations 182 6.5 LBM Numerical Scheme 184 6.6 Refining Mesh Sizes in LBM 185 6.7 Model Validation 186 6.8 Intra-Particle Concentration Distribution 187 6.9 Thermal LBM 189 6.10 Lattice Thermal Boundary Conditions 190 References 192 Chapter 7: Improved Removal of Toxic Contaminants in Water by Green Adsorbents: Nanozeolite and Metal-Nanozeolite for the Removal of Heavy Metals and Phenolic Compounds 196 7.1 Introduction 197 7.1.1 Concepts of Green Adsorbents 197 7.1.2 Surface Characteristics Modification for New Zeolite Development 198 7.1.3 Metals-Modified Zeolites 199 7.1.4 Heavy Metals Contaminants 200 7.1.5 Phenolic Contaminants 200 7.2 Preparation of Nanozeolite and Metal-Nanozeolites as Green Adsorbents 200 7.3 Physicochemical Characterization of the Green Adsorbents 201 7.3.1 Morphological Analysis 201 7.3.2 TEM Analysis 202 7.3.3 XRD Analysis 202 7.3.4 Infrared Spectra Analysis 203 7.3.5 BET Analysis 204 7.4 Removal of Heavy Metals and Organic Compounds 204 7.4.1 Removal of Heavy Metals 205 7.4.1.1 Effect of Solution pH 205 7.4.1.2 Effect of Contact Time 206 7.4.1.3 Adsorption Kinetics 208 7.4.1.4 Effect of Initial Concentration 209 7.4.1.5 Adsorption Isotherms 211 7.4.1.6 Regeneration of Heavy Metal-Loaded Adsorbents 212 7.4.1.7 Proposed Removal Mechanism 214 7.4.1.8 Adsorption Cost Estimation 215 7.4.2 Removal of Phenolic Compounds 216 7.4.2.1 Effect of Solution pH 216 7.4.2.2 Effect of Contact Time 217 7.4.2.3 Effect of Initial Concentration 217 7.4.2.4 Adsorption Isotherm 219 7.4.2.5 Regeneration of Loaded Adsorbents 219 7.4.2.6 Adsorption Mechanisms 222 7.4.2.7 Adsorption Cost Estimation 223 7.5 Summary 223 Acknowledgments 224 References 225 Chapter 8: Abiotic Removal with Adsorption and Photocatalytic Reaction 228 8.1 Introduction 229 8.1.1 Definition of Adsorption—General Perspective 229 8.1.2 Definition of Photocatalytic Reaction—General Perspective 229 8.1.3 Definition of Antibiotics 230 8.1.4 Focus on Tetracycline 231 8.1.5 Sources 233 8.2 Removal Technology 237 8.2.1 Conventional Treatment 237 8.2.2 Membrane Separation Method 238 8.2.3 Chemical Oxidation 238 8.2.4 Biodegradation 240 8.2.5 Photolysis 240 8.2.6 Adsorption Removal Method 241 8.2.6.1 Ion Adsorption 241 8.2.6.2 Carbon Material Adsorption 242 8.2.6.3 Adsorption of Other Materials 243 8.2.6.4 Adsorption/Desorption Model 243 8.2.6.5 Model for Two-Step Degradation [49] 244 8.3 Biotoxicity Assessment after Treatment 245 8.4 Amended Perspectives of Abiotic Treatment 247 8.4.1 Photocatalytic Degradation 247 8.4.2 Case Study of Adsorption 247 8.4.2.1 Effect of Initial Concentration of Pollutant and Temperature 248 8.4.2.2 Effect of Different Dosage of TiO2 in Doping and Dosage of Adsorbent Used in Solution 251 8.4.3 Analysis 253 8.4.4 Toxicity Tests 254 8.4.5 Results of Photocatalytic Degradation 254 8.4.6 Adsorption Capability 256 8.4.7 Residual Biotoxicity 257 References 259 Chapter 9: Revalorization of Agro-Food Residues as Bioadsorbents for Wastewater Treatment 264 9.1 Introduction 264 9.2 Wastewater Treatment 266 9.3 Revalorization of Agro-Food Residues as Bioadsorbents 269 9.3.1 Activated Carbon 271 9.3.2 Fruit Residues 273 9.3.2.1 Orange (Citrus) Residue 273 9.3.2.2 Other Fruit Residues 274 9.3.3 Olive (Olea Europaea) Residues 274 9.3.4 Garlic (Allium Sativum L.) Residue 279 9.3.5 Cassava (Manihot Esculenta Crantz) Residue 280 9.3.6 Cucumber (Cucumis Sativus L.) Residue 280 9.3.7 Parsley (Petroselinum Crispum) Residue 281 9.3.8 Lentils (Lens Culinaris) Residue 282 9.3.9 Apple (Malus Domestica) Residue 282 9.3.10 Corn (Zea Mays) Residue 283 9.3.11 Wheat (Triticum) Residue 283 9.3.12 Rice (Oryza) Residue 283 9.3.13 Coffee Residue 284 9.3.14 Other Residues 285 9.4 Conclusions and Future of Bioadsorption Application 286 Acknowledgments 287 References 287 Chapter 10: Adsorption on Activated Carbon: Role of Surface Chemistry in Water Purification 298 10.1 Introduction 298 10.1.1 Thermal Activation 300 10.1.2 Chemical Activation 300 10.2 Forms of Activated Carbon for Filtration Application 301 10.3 Properties of Activated Carbon 301 10.4 Surface Chemistry of Activated Carbons 303 10.5 Mechanism of Removal of Water Impurities 304 10.6 Surface Modification of Activated Carbon 305 10.7 Removal of Water Impurities by Activated Carbon 307 10.8 Removal of Monochloramine by Activated Carbon 309 10.9 Metal Impregnation for Microbial Contaminants 311 10.10 Summary 312 References 312 Index 316