Table of Contents
Preface ix
Chapter 1 Overview of Membrane-Assisted Crystallization Operations 1
1.1 Introduction 1
1.2 Timeline of the Development of Membrane-Assisted Crystallization Processes 2
1.3 Dialysis 4
1.4 FO 5
1.4.1 Related equations 6
1.5 Pressure-Driven Membrane Processes 9
1.5.1 Mass balances 10
1.5.2 Membrane transport 11
1.5.3 Concentration polarization 13
1.5.4 Steady-state equations 15
1.5.5 Crystallization equations 16
1.5.6 Energetic aspects 17
1.6 Membrane Distillation (MD) and Osmotic Distillation (OD) 20
1.6.1 Solvent evaporation membrane crystallizer 22
1.6.2 Antisolvent membrane crystallizer 23
1.6.3 General advantages of MCr 24
1.7 Other Membrane-Assisted Crystallization Configurations 26
1.7.1 Membrane contactors (MCs) 26
1.7.2 Membrane reactors (MRs) 27
1.7.3 Antisolvent pressure-driven membrane-assisted crystallization 29
1.7.4 Supported liquid membranes (SLMs) 30
1.8 Membrane Templates (MTs) 31
References 32
Chapter 2 Theoretical Aspects in Membrane Crystallization 39
2.1 Introduction 39
2.2 Mass Transfer 39
2.2.1 Mass transfer across the membrane 40
2.2.2 Boundary layer resistances 42
2.2.3 Driving force to mass transfer 44
2.3 Heat Transfer 51
2.3.1 Boundary layer resistance and temperature polarization 52
2.3.2 Heat transfer across the membrane 54
2.4 Influence of Membrane Morphology on Nucleation Rate 56
2.4.1 Effect of contact angle 56
2.4.2 Effect of membrane porosity 60
2.4.3 Effect of membrane roughness 63
2.4.4 Effect of the chemistry of surfaces 66
References 72
Chapter 3 Membrane Materials 77
3.1 Introduction 77
3.2 Membrane Polymers 77
3.2.1 Polytvinylidene fluoride) 80
3.2.2 Poly(tetrafluoroethylene) 81
3.2.3 Poly(ethylenechlorotrifluoroethylene) 83
3.2.4 Other fluoropolymers 84
3.3 Preparation Methods 84
3.3.1 Sintering 85
3.3.2 Stretching 86
3.3.3 Track-etching 88
3.3.4 Phase inversion technique 88
3.4 Membrane Modification 101
3.4.1 Additives in the casting solution 101
3.4.2 Use of copolymers 103
3.4.3 Composite membranes 104
3.4.4 Surface modifying molecules 105
3.5 Hydrophobic/Hydrophilic Properties, Contact Angle, Surface Tension 105
3.5.1 Contact angle 105
3.5.2 Good-van Oss-Chaudhury method 107
3.5.3 Contact angle and wettability 109
3.6 The Influence of Pore Size Distribution 110
References 112
Chapter 4 Membrane Crystallization of Inorganic Compounds 119
4.1 Introduction 119
4.2 Product Characterization: Shape and CSD 121
4.3 Kinetic Aspects: The Mixed-Suspension Mixed-Product Removal (MSMPR) Model 126
4.4 Growth Rate 129
4.5 Applications 132
4.5.1 Treatment of brines 132
4.5.2 Reactive gas-liquid (G-L) membrane crystallization 139
4.5.3 Treatment of wastewater streams 146
References 147
Chapter 5 Morphology, Polymorphism, and Co-Crystallization of Molecular Compounds 151
5.1 Introduction 151
5.2 The Metastable Zone 153
5.3 Crystal Morphology 154
5.4 Polymorphism 155
5.4.1 Definitions 155
5.4.2 Phase diagram of polymorphs 156
5.4.3 Polymorph selection 159
5.5 Polymorphism and Drugs 164
5.6 Current Strategies for Obtaining the Desired Polymorph 165
5.7 Controlling Polymorphism by Membrane-Assisted Crystallization 166
5.7.1 Glycine 166
5.7.2 Paracetamol 171
5.7.3 Carbamazepine 177
5.7.4 Effect of supersaturation control in membrane crystallization on polymorph selectivity 178
5.8 Production of Pharmaceutical Co-Crystals 180
5.8.1 Dependence on initial solution composition 181
5.8.2 Study of phase equilibrium diagram 182
References 185
Chapter 6 Crystallization of Biomacromolecules 193
6.1 Introduction 193
6.2 Interest in Protein Crystallization 193
6.3 Difficulties in Obtaining Protein Crystals 194
6.4 Regulation of Supersaturation Rate in Membrane-Assisted Crystallization of Proteins 196
6.5 Influence of Supersaturation Control on Crystallization Kinetics 201
6.5.1 Monitoring nucleation and crystal growth rates by the turbidity method 202
6.5.2 Kinetic parameters 204
6.6 Heterogeneous Nucleation by Porous Membranes 207
6.7 Energetics of Protein Nucleation on Polymeric Membranes 212
6.7.1 Ising model 213
6.8 Growing Proteins in Forced Solution Convection 219
6.8.1 Crystal growth in dynamic membrane crystallizers 221
6.8.2 Effect of the forced solution convection on the crystal growth rate 222
References 224
Index 229
