Solvent Extraction: Classical and Novel Approaches Vladimir S. Kislik Casali Institute of Applied Chemistry The Hebrew University of Jerusalem Campus Givat Ram, Jerusalem 91904, Israel rrr?-rj Amsterdam boston heidelberg London. new york oxford riloiivliik Paris san dieco. san francisco. Singapore. Sydney tokyo
f Contents Preface Introduction xi xiii Part I Conventional (Classical) Principles of Solvent Extraction and Practice 1. Modern (Classical) Fundamental Principles of Solvent Extraction 3 1. Introduction 5 2. Solvent Extraction By Solvation 5 3. Solvent Extraction with Chemical Reactions (By Complexation) 12 4. Driving Forces of Solvent Extraction 15 5. Influence of Kinetics Factors 17 6. Selectivity 34 7. Factors Affecting Extraction Process 36 8. Module Design Considerations 49 Determination of Distribution Ratios 55 9. Experimental 10. Summarizing Remarks 58 References 63 2. Principles of Solvent Extraction of Organic and Mineral Acids 69 1. Introduction 69 2. Extraction of Acids by Carbon-Bonded Oxygen-Donor Extractants and Substituted Hydrocarbon Solvents 71 3. Phosphorus-Bonded Oxygen Donor Extractants 85 4. Aliphatic Amine Extractants 89 5. Extraction of Strong (Inorganic) Acids 98 6. Summarizing Remarks 102 References 108 3. Chemistry of Metal Solvent Extraction 113 1. Introduction 114 2. Metal Extraction by Cation Exchangers (Acidic Extractants) 114 3. Metal Extraction by Anion Exchangers (Ion Pair Formation) 127
GD Contents 4. Extraction Through Formation of H-Bonding and Solvating Complexes 135 5. Extraction Through Mixed Complex Formation 144 6. Extractable Complexation of Monovalent Metals 150 7. Extraction with Aqueous Biphasic Systems 151 References 153 4. Engineering Development of Solvent Extraction Processes 157 1. Introduction 157 2. Extraction Stage 159 3. Stripping Organic Solutions 169 4. Extraction Efficiency 170 5. Equipment Design for Continuous Extraction-Stripping Processes 173 6. Solvent Losses 182 7. Economical Considerations 183 8. Problems with Scale-Up to Industrial Systems 183 References 184 5. Examples of Application of Solvent Extraction Techniques in Chemical, Radiochemical, Biochemical, Pharmaceutical, Analytical Separations, and Wastewater Treatment 185 1. Introduction 188 2. Extraction in Hydrometallurgy (Metals Extraction) 189 3. Solvent Extraction in Nuclear Chemistry and Technology 218 4. Solvent Extraction in Analytical Chemistry 239 5. Application of Solvent Extraction in Biochemical and Pharmaceutical Separations 273 6. Application of Solvent Extraction in Organic and Biofuels Separation 278 7. Solvent Extraction in Recovery of Waste and Wastewater Treatment 284 References 297 Part II Novel Competitive Complexation/Solvation Theory (CCST) of Solvent Extraction: Principles and Practice 6. Backgrounds of the Competitive Complexation/ Solvation Theory of Solvent Extraction 317 1. Introduction 317
Contents GD 2. Complexation Through the H-Bonding and Proton Transfer 317 3. Distribution Isotherm 319 4. Modified Competitive Preferential Solvation Theory 323 5. Electronic Acid-Base Theory and Amphoterity 327 6. Aggregation 328 References 329 7. Competitive Complexation/Solvation Theory of Solvent Extraction: General Mechanisms and Kinetics 335 1. Basic Statements 335 2. Extraction Systems with Low Solute Concentrations in Organic Phase 336 3. Systems with Medium Concentrations of the Solute 345 4. Systems with High Solute Concentrations 348 5. Comparison of Conventional and Presented Theories Description 350 6. Summarizing Remarks for the CCST 351 References 352 8. CCST in Engineering Design, Procedures, and Calculations 355 1. Introduction 355 2. Engineering Considerations in Experimental Investigation of CCST 356 3. Experimental Techniques for the Presented Theory 358 4. Determination of Extraction Constant and its Comparison with CCST Affinity Constant Ratios 361 5. Analytical Methods Used for the CCST Verification 363 6. Transferability of the Values of Affinity Constant Ratios 364 References 364 9. The CCST in Solvent Extraction of Acids by Amine-Based Extractants 367 1. Introduction 367 2. Acid-Amine Systems in the CCST Interpretation 372 3. The Systems with Active Solvent as an Additive 381 4. Experimental Application of the CCST in Carboxylic Acids Extraction 384 5. Summarizing Remarks 395 References 397
yjii ^) Contents 10. Competitive Complexation/Solvation Theory in Metal Solvent Extraction 399 1. Introduction 399 2. CCST Basic Statements 400 3. Mathematical Supplement for the CCST in Metal Extraction 415 4. Experimental Verification of the CCST Approach 423 5. Summarizing Remarks 427 References 428 11. Final Remarks on the Competitive Complexation/ Solvation Theory of Solvent Extraction and its Application 433 Part III Modern and Future Trends in Fundamentals and Applications of Solvent Extraction 12. Modern and Future Trends in Fundamentals of Solvent Extraction 439 1. Introduction 439 2. Novel Molecular Models Theoretical Approach 440 3. Low Energy Reactions Measurement 442 4. Expected Advances in Kinetics Studies 442 5. Supramolecular (SUPRAS) Theoretical Approach 443 References 449 13. Advances in Development for Liquid-Liquid of Solvents Extraction 451 1. Introduction 452 2. Organic Solvents 453 3. Water as a Solvent 457 4. Renewable Water-Based Solvents 458 5. Ionic as Liquids Solvents for Extraction 465 6. Amphiphilic Compounds (Supramolecules) as Solvents in Solvent Extraction 467 7. Extraction by Microemulsion 471 8. Recovery of Reagents 474 9. Future Trends in the Development of New Solvents 475 10. Concluding Remarks 477 References 478
Contents 14. Recent Advances in Solvent Extraction Processes and Techniques 483 1. Introduction 484 2. Equipment Design and Scale-Up 3. Supercritical Considerations 485 Fluid Extraction 486 4. Subcritical Water Extraction 493 5. Aqueous Two-Phase Systems 498 6. Extraction Processes with Ionic Liquids 499 7. Liquid Membrane and Nondispersive, Membrane-Based Solvent Extraction Techniques 501 8. Supramolecular-Based Extraction Techniques 504 9. Solid-Liquid Extraction Systems 511 10. Assisted Solvent Extraction 513 11. Extraction of Gas in Analytical Applications 514 References 515 Appendix 525 Index 539