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CONTENTS
PREFACE v
About the Author vi
CONTENTS vii
INTRODUCTION – Sorption and Biosorption Share the Methodology 1
1.1 METALS:
ENVIRONMENTAL THREAT 5
1.2 BIOSORPTION TECHNOLOGY 7
1.3 BIOSORPTION ENTERPRISE 9
Techno-Economic
Basis 11
Identification
of Potential Synergies and Partners 11
1.4 CONCLUSION 12
2.1 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 23
2.2 Adsorption - Uptake 25
2.3 Desorption 27
2.4 Mechanism of metal biosorption 29
2.5 Modeling 30
2.6 Granulation 31
Biosorption Process operation 32
2.7 Project disciplines and Tasks 33
3. THE MECHANISM OF METAL
BIOSORPTION 35
3.1 Biosorption
and Bioaccumulation 35
3.2 CHEMICAL BINDING 36
Complexation, Coordination,
Chelation of Metals 36
Ion Exchange, Adsorption 39
Inorganic Microprecipitation 40
3.3 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
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 54
3.5 REFERENCES 57-58
4.1 The Choice of Metals 59
4.1-1 Removal of Toxic Heavy Metals 60
“The
Big Three” 60
Second-Tier
Toxic Heavies 60
Radionuclides 60
4.2 INDUSTRIAL ENVIRONMENTAL THREATS 61
4.2-1 Electroplating Operations 61
4.2-2 Mining Industry Effluents 63
Acid Mine
Drainage 63
4.2-3 Power-Generating Stations 65
4.3 RECOVERY OF METALS 67
4.3-1 Precious Metals 67
4.3-2 Strategic Metals 67
4.3-3 Rare Earth Elements 68
Chemical
Properties of REE 69
4.3-4 Metal Removal/Recovery Priorities 71
4.4 METAL BEHAVIOR IN SOLUTION 72
4.4-1 Chromate in Solution 73
4.4-2 Vanadate in Solution 73
4.4-3 Gold-Cyanide in Solution 74
4.4-4 Example of Uranium speciation in solution 75
4.4-5 MINEQL+ 78
4.5 REFERENCES 80
5.1 BIOMASS TYPES 81
5.1-1 References 83-84
5.2 SORPTION BY CHITINOUS BIOMASS 85
5.2-1 Properties and Composition of Crab
Shells 85
5.2-2 Main Biomolecules in Crab Shells 86
Chitin 86
Protein 87
Chitin-Protein Complex 87
5.3 BIOSORPTION BY ALGAL BIOMASS 88
5.3-1 Seaweed Cell
walls 89
5.3-2 Main Biomolecules
in Seaweeds 91
Cellulose 91
Alginic
Acid 92
Fucoidan 93
5.3-3 Sulfated
Galactans of Red Algae 93
Agar 93
Porphyran 94
Carrageenan 94
5.3-4 The mechanism of biosorption by marine algae 94
Importance
of ion exchange
Relevance of
complexation and electrostatic attraction 95
5.4 SORPTION BY MICROBIAL BIOMASS 95
5.4-1 Biosorption by Bacteria 95
5.4-2 Biosorption by Fungi 97
5.5 REFERENCES 100-102
6. EQUILIBRIUM BIOSORPTION
PERFORMANCE 103
6.1 Sorption
Equilibrium 103
6.1-1 Single-Sorbate Isotherms 105
Simple Sorption Models 105
Langmuir model 105
Freundlich model 106
Other sorption isotherm relationships 107
6.1-2 Comparison of Sorption Performance 108
6.1-3 Equilibrium Constants 110
6.1-4 Experimental Sorption Isotherm 112
The tea-bag experiment 114
Sorbent Comparison Based on % Removal 114
6.1-5 REFERENCES 116
6.1-6 Ion Exchange Isotherms and Separation
Factors 117
Ion Exchange Equilibrium
Relationships 118
Example of Biosorbent Ion Exchange 120
REFERENCES 120
6.2 MULTI-SORBATE Sorption Equilibrium (3-D) 121
6.2-1 Sorption Isotherms with a Parameter 121
6.2-2 Sorption Isotherm Plots 123
6.2-3 Cutting of Sorption Isotherm 123
6.2-4 Example of the Fe-Cd Sorption System 125
6.2-5 BIBLIOGRAPHY 126
6.3 MODELING OF EQUILIBRIUM
BIOSORPTION 127
6.3-1 Types of Sorption Models 129
Models
Considering Ideality 130
6.3-2 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
ii) In the Solid Phase 139
Surface Complex Model 139
Donnan Model 140
Wilson Model for Ion Exchange 140
6.3-3 Two Binding Sites 142
6.3-4 Considering the effect of Ionic
Strength: Donnan Model 144
Incorporating
sorption particle swelling 145
6.3-5 Combination
of the Isotherm and Donnan Models 146
Calculation Without Iterations 146
6.3-6 Summary 148
6.3-7 REFERENCES 149-150
6.4 EQUILIBRIUM MODEL WITH SOLUTION CHEMISTRY 151
6.4-1 HIEM
model for Uranium Biosorption Isotherm 151
6.4-2 Determination of HIEM model parameters
and modeling of experimental data 159
6.4-3 Comparison of experimental uranium isotherms
and HIEM calculations at
different solution pH values 162
6.4-5 Summary 163
6.4-6 REFERENCES 164
6.5 BIOSORPTION BATCH DYNAMICS 165
6.5-1 End-Point Titration Curves 166
6.5-2 Eliminating External Mass Transfer 166
6.5-3 Biosorbent Particle Size and Sorption Rate 167
6.5-4 Rate of Uptake and Proton Release 169
6.5-5 Mass Transfer Model for Biosorption Rate 170
6.5-6 Numerical Solution of the Model Equations 172
6.5-7 Regression of Model Parameters 174
6.5-8 Desorption Rate 176
6.5-9 REFERENCES 178
7. BIOSORPTION PROCESS
PRINCIPLES 179
CONTINUOUS-FLOW
REACTOR/CONTACTOR SYSTEMS 179
7.1 The Fixed-Bed Column Sorption System 180
7.2 The Fluidized Bed Column Sorption System 181
7.3 The Completely Mixed Solid-Liquid Sorption System 181
7.4 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 186
7.5 Process Example 187
Specifications 187
Mass
Balances 188
Sizing 189
8. modeling of column performance 191
8.1 REVIEW: CFFB Sorption Column Performance Modeling 191
REFERENCES 196
8.2 (ECM) EQUILIBRIUM COLUMN MODEL 197
Symbols 198
Equilibrium Considerations 198
Defining Characteristics of the ECM 199
8.2-1 Basic concepts of ECM and symbol conventions 199
ECM Equations for Transitions 201
8.2-2 Calculation of Concentration Histories for
Column Effluent 203
Effects of Competitive Ion Exchange on the
Performance
of sorption Columns 203
8.2-3 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 208
8.2-4 Conclusions on the ECM Concept 210
8.2-5 REFERENCES 212
8.3 (MTM) COLUMN SORPTION
MODEL WITH MASS TRANSFER 213
Symbols 214
8.3-1 Connection
between Equilibrium and Dynamic Sorption 215
Start
with Equilibrium Considerations 215
8.3-2 Fitting the Equilibrium Model and Ion
Exchange Isotherms 219
8.3-3 Fitting and Use of the Sorption Column Model 219
8.3-4 Example
of the MTM Use 220
8.3-5 Conclusions
on the MTM concept 221
8.3-6 REFERENCES 222
8.4 DERIVATION OF MASS
TRANSFER MODEL FOR SORPTION COLUMS 223
8.4-1 Axial
Dispersion – Experimental Evaluation 223
8.4-2 Model Derivation 224
8.4-3 Numerical Solution of the Model Equations 227
8.4-4 Determination of Model Parameters and Data
Modeling 229
8.4-5 REFERENCES 232
9. BIOSORBENT MATERIAL
PREPARATION 233
9.1
Biomass Sources 233
Industrial Biomass 234
Seaweeds 234
9.2 Characterization of Biosorbent Particles 235
Particle Size 235
Particle Shape 236
Porosity 236
Mechanical Strength 237
Density and Swelling 237
9.3 Biosorbent Material Formulation 238
9.3-1 Biomass Reinforcement 238
9.3-2 Crosslinking Procedures 240
Formaldehyde and Urea Formaldehyde
Crosslinking 242
Experimental
Crosslinking Examples 243
9.3-3
Granulation Techniques 244
Extrusion 244
Fluidized Bed Granulation 244
Spray Drying 245
9.4 Column Pressure Drop 246
9.5 Conclusion to Processing 247
9.6 Desorption 248
9.6-1 Choice of Ionic Form of Sorbent 250
9.6-2 Pre-treatment of Sargassum biomass 251
Leaching
of organic material and active sites 251
Biosorbent
Stability and Metal Affinities 252
9.7 REFERENCES 253-254
10. MONOCLONAL
ANTIBODIES BIOSORPTION 255
10.1 ‘Silver Bullet’ Biosorption 255
10.2 Production of Monoclonal Antibodies 257
In vitro Production Methods 259
10.3 Purification and Application of mAbs 260
Ion Exchange Chromatography 261
Hydrophobic Interaction Chromatography 261
Gel Filtration Chromatography 262
Affinity Chromatography 262
Large Scale Purification 265
10.4 The Future: Monoclonal vs. Single Domain
Antibodies 267
10.5 Summary of mAbs Work Cited (Table 10-3) 268
10.6 REFERENCES 270-273
11. Biosorption Publications – McGill University Research
Group 275
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 293-299
13. LIST OF FIGURES and TABLES 301-312