PREFACE About the Author

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Joel McCormick
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1 Contents / vii CONTENTS PREFACE About the Author CONTENTS v vi vii INTRODUCTION Sorption and Biosorption Share the Methodology 1 1. POTENTIAL OF BIOSORPTION METALS: ENVIRONMENTAL THREAT BIOSORPTION TECHNOLOGY BIOSORPTION ENTERPRISE 9 Techno-Economic Basis 11 Identification of Potential Synergies and Partners CONCLUSION BIOSORPTION R&D Biomass Screening where to look and why? 14 What are Biosorbents? 16 Biosorption Performance 17 Biosorbent Metal Selectivity 18 Review of Biosorption Performance 19 REFERENCES Adsorption - Uptake Desorption Mechanism of metal biosorption Modeling Granulation 31 Biosorption Process operation Project disciplines and Tasks THE MECHANISM OF METAL BIOSORPTION BIOSORPTION AND BIOACCUMULATION CHEMICAL BINDING 36 Complexation, Coordination, Chelation of Metals 36 Ion Exchange, Adsorption 39 Inorganic Microprecipitation THE MECHANISM OF BIOSORPTION 41 Temperature Effect 41 Influence of ph 42 Ionic Strength Effect 43 Presence of Other Anions 43 Overall Mechanisms: Ion Exchange, Adsorption, Microprecipitation 44 Contribution of Electrostatic Attraction and Complexation 45 Binding Sites 46

2 viii / SORPTION & BIOSORPTION 3.4 INSTRUMENTAL ANALYSES 48 FTIR Analysis Cation Deposition 49 FTIR Analysis Anion Deposition 52 Chromate Biosorption 52 Vanadate Biosorption 53 Gold-Cyanide Biosorption 54 Determination of Electrostatic Attraction 54 Combination Mechanisms REFERENCES METALS IN BIOSORPTION THE CHOICE OF METALS Removal of Toxic Heavy Metals 60 The Big Three 60 Second-Tier Toxic Heavies 60 Radionuclides INDUSTRIAL ENVIRONMENTAL THREATS Electroplating Operations Mining Industry Effluents 63 Acid Mine Drainage Power-Generating Stations RECOVERY OF METALS Precious Metals Strategic Metals Rare Earth Elements 68 Chemical Properties of REE Metal Removal/Recovery Priorities METAL BEHAVIOR IN SOLUTION Chromate in Solution Vanadate in Solution Gold-Cyanide in Solution Example of Uranium speciation in solution MINEQL REFERENCES SORPTION BY BIOMASS BIOMASS TYPES References SORPTION BY CHITINOUS BIOMASS Properties and Composition of Crab Shells Main Biomolecules in Crab Shells 86 Chitin 86 Protein 87 Chitin-Protein Complex BIOSORPTION BY ALGAL BIOMASS Seaweed Cell walls Main Biomolecules in Seaweeds 91 Cellulose 91 Alginic Acid 92 Fucoidan 93

3 Contents / ix Sulfated Galactans of Red Algae 93 Agar 93 Porphyran 94 Carrageenan The mechanism of biosorption by marine algae 94 Importance of ion exchange Relevance of complexation and electrostatic attraction SORPTION BY MICROBIAL BIOMASS Biosorption by Bacteria Biosorption by Fungi REFERENCES EQUILIBRIUM BIOSORPTION PERFORMANCE SORPTION EQUILIBRIUM Single-Sorbate Isotherms 105 Simple Sorption Models 105 Langmuir model 105 Freundlich model 106 Other sorption isotherm relationships Comparison of Sorption Performance Equilibrium Constants Experimental Sorption Isotherm 112 The tea-bag experiment 114 Sorbent Comparison Based on % Removal REFERENCES Ion Exchange Isotherms and Separation Factors 117 Ion Exchange Equilibrium Relationships 118 Example of Biosorbent Ion Exchange 120 REFERENCES MULTI-SORBATE SORPTION EQUILIBRIUM (3-D) Sorption Isotherms with a Parameter Sorption Isotherm Plots Cutting of Sorption Isotherm Example of the Fe-Cd Sorption System BIBLIOGRAPHY MODELING OF EQUILIBRIUM BIOSORPTION Types of Sorption Models 129 Models Considering Ideality Sorption Reactions and Modeling 132 Multi-Component Langmuirian Models 133 Symbols 134 Langmuirian Models with Equilibrium Constants 135 Considering also the electrostatic binding 136 Considering the effect of ph 137 Models Considering Non-Ideality 138 i) In the Liquid Phase Only 138

4 x / SORPTION & BIOSORPTION ii) In the Solid Phase 139 Surface Complex Model 139 Donnan Model 140 Wilson Model for Ion Exchange Two Binding Sites Considering the effect of Ionic Strength: Donnan Model 144 Incorporating sorption particle swelling Combination of the Isotherm and Donnan Models 146 Calculation Without Iterations Summary REFERENCES EQUILIBRIUM MODEL WITH SOLUTION CHEMISTRY HIEM model for Uranium Biosorption Isotherm Determination of HIEM model parameters and modeling of experimental data Comparison of experimental uranium isotherms and HIEM calculations at different solution ph values Summary REFERENCES BIOSORPTION BATCH DYNAMICS End-Point Titration Curves Eliminating External Mass Transfer Biosorbent Particle Size and Sorption Rate Rate of Uptake and Proton Release Mass Transfer Model for Biosorption Rate Numerical Solution of the Model Equations Regression of Model Parameters Desorption Rate REFERENCES BIOSORPTION PROCESS PRINCIPLES 179 CONTINUOUS-FLOW REACTOR/CONTACTOR SYSTEMS The Fixed-Bed Column Sorption System The Fluidized Bed Column Sorption System The Completely Mixed Solid-Liquid Sorption System Fundamental Aspects of the Continuous-Flow Fixed-Bed Column 183 The Breakthrough Curve and its Interpretation 183 The link between equilibrium and column breakthrough 184 Ion Exchange with Mixed Sorbates 185 Sorption Process Optimization Challenge Process Example 187 Specifications 187 Mass Balances 188 Sizing MODELING OF COLUMN PERFORMANCE REVIEW: CFFB Sorption Column Performance Modeling 191 REFERENCES 196

5 Contents / xi 8.2 (ECM) EQUILIBRIUM COLUMN MODEL 197 Symbols 198 Equilibrium Considerations 198 Defining Characteristics of the ECM Basic concepts of ECM and symbol conventions 199 ECM Equations for Transitions Calculation of Concentration Histories for Column Effluent 203 Effects of Competitive Ion Exchange on the Performance of sorption Columns Case Study 204 a) Theory of overshoots in ternary systems 204 b) Agreement between overshoots predicted by the ECM and experiments 205 c) Assessment of overshoots in a biosorption process removing Cu from wastewater containing traces of Cd or Zn 207 The Use of ECM to Determine the Elution Order of Metals and the Column Service Time for Multi-Metal Mixtures Conclusions on the ECM Concept REFERENCES (MTM) COLUMN SORPTION MODEL WITH MASS TRANSFER 213 Symbols Connection between Equilibrium and Dynamic Sorption 215 Start with Equilibrium Considerations Fitting the Equilibrium Model and Ion Exchange Isotherms Fitting and Use of the Sorption Column Model Example of the MTM Use Conclusions on the MTM concept REFERENCES DERIVATION OF MASS TRANSFER MODEL FOR SORPTION COLUMS Axial Dispersion Experimental Evaluation Model Derivation Numerical Solution of the Model Equations Determination of Model Parameters and Data Modeling REFERENCES BIOSORBENT MATERIAL PREPARATION Biomass Sources 233 Industrial Biomass 234 Seaweeds Characterization of Biosorbent Particles 235 Particle Size 235 Particle Shape 236 Porosity 236 Mechanical Strength 237 Density and Swelling 237

6 xii / SORPTION & BIOSORPTION 9.3 Biosorbent Material Formulation Biomass Reinforcement Crosslinking Procedures 240 Formaldehyde and Urea Formaldehyde Crosslinking 242 Experimental Crosslinking Examples Granulation Techniques 244 Extrusion 244 Fluidized Bed Granulation 244 Spray Drying Column Pressure Drop Conclusion to Processing Desorption Choice of Ionic Form of Sorbent Pre-treatment of Sargassum biomass 251 Leaching of organic material and active sites 251 Biosorbent Stability and Metal Affinities REFERENCES MONOCLONAL ANTIBODIES BIOSORPTION Silver Bullet Biosorption Production of Monoclonal Antibodies 257 In vitro Production Methods Purification and Application of mabs 260 Ion Exchange Chromatography 261 Hydrophobic Interaction Chromatography 261 Gel Filtration Chromatography 262 Affinity Chromatography 262 Large Scale Purification The Future: Monoclonal vs. Single Domain Antibodies Summary of mabs Work Cited (Table 10-3) REFERENCES BIOSORPTION PUBLICATIONS McGill University Research Group APPENDICES 279 Appendix A Matlab Code for HIEM Model 279 Appendix B Fortran Code for Galerkin Finite Element Method 281 Appendix C Fortran Code for Orthogonal Collocation Method 285 Appendix D Matlab Subroutines for Column Concentration Profiles LIST OF FIGURES and TABLES INDEX

LIST OF FIGURES (slides) and TABLES

List of Figures and Tables / 301 13 LIST OF FIGURES (slides) and TABLES INTRO Sorption and Biosorption Figure i-1 The two phenomena differ only in the type of the solid sorbent material employed Figure