Con tents

1. Introduction
1
2. Historical Perspective
17
3. Phase Diagrams for Supercritical Fluid-Solute Mixtures
27
Phase Diagrams for Binary Mixtures
31
Solid-Supercritical Fluid Phase Diagrams
45
Polymer-Supercritical Fluid Phase Diagrams
61
Phase Diagrams for Ternary Mixtures
71
4. Experimental Techniques in High-pressure Studies
85
Dynamic Methods for Measuring Solubilities in Supercritical
Fluids
85
Static Methods for Measuring Solubilities in Supercritical Fluids
Methods for Determining Phase Border Cunies
94
5. Thermodynamic Modeling of Supercritical Fluid-Solute Phase
Behavior
99
Intermolecular Forces
99
Solubility Parameters
105
Vapor-Liquid Calculations
110
Liquid-Liquid-Vapor Calculations
114
Polymer-Supercritical Fluid Calculations
120
Solid-Supercritical Fluid Calculations
127
6. Process Operations
135
7. Early Industrial Applications
145
Propane Deasphalting
145
Solexol Process
150
ROSE Process
153
8. Supercritical Fluid Process Development Studies
157
Activated Carbon Regeneration
158
Separation of Organic-Water Solutions
170
Breaking an Azeotrope
182
9. Polymers and Monomers Processing
189
High-pressure Polyethylene Polymerization
189
Polymer Fractionation Processes
192
Polyethylene Fractionation
198

91

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Contents

Fractionation of Ethylene-Based Copolymers

205
Polysiloxane and Polysiloxane/PMMA Copolymer
Fractionation
217
Fractionation of Polymer Binders for Solid Propellants
250
Oligomer Extraction from Polymers
257
Supercritical Fluid Chromatography Analysis of Polystyrene
258
Polymer Fiber Spinning
260
Fractionation of Various Polymers
262
Polymer-Organic Solvent Phase Separation
280
Monomer Purification
285
10. Processing Pharmaceuticals, Natural Products, Specialty Chemicals, and
Waste Streams
293
Coffee Decaffeination
294
Edible Oils Extraction
299
304
Extraction of Chemotherapeutic Agents
Isomer Separations
307
Treatment of Waste Streams
309
11. Chemical Reactions in Supercritical Fluids
311
Enzyme Reactions
311
High-Temperature Reactions
321
Heterogeneous Catalysis
322
Viscosity Effects
325
Reaction/Separation Schemes
326
Enhanced Reaction Rates and Selectivities
328
12. Special Applications
333
Supercritical Fluid Nucleation
333
GAS Antisolvent Recrystallization
342
Swelling of Polymers
357
360
Formation of Porous Polymers
13. Epilogue
367
References
373
Appendix A. Patent Reviews
395
1. The Zosel Patent
397
2. Petroleum and other Fossil Fuels
Separations
399
3. Coffee Decaffeination
417
4. Extraction of other Vegetable and Animal
Materials
427
5. Polymers Processing
441
6. Separation of Organic-Water Solutions
444
7. Materials Processing
449
8. Miscellaneous
453
Appendix B . Calculating Binary, Vapor-Liquid Equilibria using the PengRobinson Equation of State
463

Contents

vii

Calculating Ternary, Vapor-Liquid Equilibria using the PengRobinson Equation of State

470
Calculating Ternary, Vapor-Liquid-Liquid Equilibria using the
478
Peng-Robinson Equation of State
Calculating Binary, Solid-SCF or Solid-Liquid-Gas Equilibria
using the Peng-Robinson Equation of State
487
Calculating Binary, Vapor-Liquid Equilibria using the SanchezLacombe Equation of State
492
Calculating Polymer-Solvent-Solvent, Vapor-Liquid Equilibria
497
using the Sanchez-Lacombe Equation of State
Calculating Polymer-Solvent-Solvent, Vapor-Liquid-Liquid
Equilibria using the Sanchez-Lacombe Equation of
State
500
Index

503