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Membrane Processes. Pervaporation, Vapor Permeation and Membrane Distillation for Industrial Scale Separations. Edition No. 1

  • Book

  • 504 Pages
  • February 2019
  • John Wiley and Sons Ltd
  • ID: 5226965

A reference for engineers, scientists, and academics who want to be abreast of the latest industrial separation/treatment technique, this new volume aims at providing a holistic vision on the potential of advanced membrane processes for solving challenging separation problems in industrial applications.

Separation processes are challenging steps in any process industry for isolation of products and recycling of reactants. Membrane technology has shown immense potential in separation of liquid and gaseous mixtures, effluent treatment, drinking water purification and solvent recovery. It has found endless popularity and wide acceptance for its small footprint, higher selectivity, scalability, energy saving capability and inherent ease of integration into other unit operations. There are many situations where the target component cannot be separated by distillation, liquid extraction, and evaporation. The different membrane processes such as pervaporation, vapor permeation and membrane distillation could be used for solving such industrial bottlenecks.

This book covers the entire array of fundamental aspects, membrane synthesis and applications in the chemical process industries (CPI). It also includes various applications of pervaporation, vapor permeation and membrane distillation in industrially and socially relevant problems including separation of azeotropic mixtures, close-boiling compounds, organic-organic mixtures, effluent treatment along with brackish and seawater desalination, and many others. These processes can also be applied for extraction of small quantities of value-added compounds such as flavors and fragrances and selective removal of hazardous impurities, viz., volatile organic compounds (VOCs) such as vinyl chloride, benzene, ethyl benzene and toluene from industrial effluents.

Including case studies, this is a must-have for any process or chemical engineer working in the industry today. Also valuable as a learning tool, students and professors in chemical engineering, chemistry, and process engineering will benefit greatly from the groundbreaking new processes and technologies described in the volume.

Table of Contents

Preface xvii

1 Tackling Challenging Industrial Separation Problems through Membrane Processes 1
Siddhartha Moulik, Sowmya Parakala and S. Sridhar

1.1 Water: The Source of Life 2

1.2 Significance of Water/Wastewater Treatment 5

1.3 Wastewater Treatment Techniques 8

1.4 Membrane Technologies for Water/Wastewater Treatment 11

1.5 Membranes: Materials, Classification and Configurations 12

1.5.1 Types of Membranes 12

1.5.1.1 Symmetric Membranes 12

1.5.1.2 Asymmetric Membranes 13

1.5.1.3 Electrically Charged Membranes 14

1.5.1.4 Inorganic Membranes 14

1.5.2 Membranes Modules and Their Characteristics 14

1.6 Introduction to Membrane Processes 17

1.6.1 Conventional Membrane Processes 17

1.7 CSIR-IICT’s Contribution for Water/Wastewater Treatment 21

1.7.1 Nanofiltration Plant for Processing Coke Oven Wastewater in Steel Industry 22

1.8 Potential of Pervaporation (PV), Vapor Permeation (VP), and Membrane Distillation (MD) in Wastewater Treatment 24

1.9 Conclusion 32

References 33

2 Pervaporation Membrane Separation: Fundamentals and Applications 37
Siddhartha Moulik, Bukke Vani, D. Vaishnavi and S. Sridhar

2.1 Introduction and Historical Perspective 38

2.2 Principle 40

2.2.1 Mass Transfer 42

2.2.2 Factors Affecting Membrane Performance 44

2.3 Membranes for Pervaporation 45

2.4 Applications of Pervaporation 46

2.4.1 Solvent Dehydration 46

2.4.2 Organophilic Separation 55

2.4.2.1 Removal of VOCs 57

2.4.2.2 Extraction of Aroma Compounds 58

2.4.3 Organic/Organic Separation 64

2.4.3.1 Separation of Polar/Non-Polar Mixture 64

2.4.3.2 Separation of Aromatic/Alicyclic Mixtures 70

2.4.3.3 Separation of Aromatic/Aliphatic/Aromatic Hydrocarbons 71

2.4.3.4 Separation of Isomers 72

2.5 Conclusions and Future Prospects 77

References 78

3 Pervaporation for Ethanol-Water Separation and Effect of Fermentation Inhibitors 89
Anjali Jain, Sushant Upadhyaya, Ajay K. Dalai and Satyendra P. Chaurasia

3.1 Introduction 90

3.2 Theory of Pervaporation 91

3.2.1 Applications of Pervaporation 92

3.2.2 Advantages of Pervaporation 93

3.2.3 Pervaporation Performance Evaluation Parameters 93

3.3 Various Membranes Used for the Recovery of Ethanol 94

3.3.1 Organic Membranes 94

3.3.2 Inorganic Membranes 102

3.3.3 Mixed Matrix Membranes 104

3.4 Effects of Process Variables on Ethanol Concentration in PV 106

3.4.1 Effect of Feed Flow Rate 106

3.4.2 Effect of Ethanol Concentration in Feed 107

3.4.3 Effect of Feed Temperature 108

3.4.4 Effect of Permeate Pressure 109

3.5 Effect of Fermentation Inhibitors on Pervaporation Performance 109

3.5.1 Effect of Furfural Concentration 112

3.5.2 Influence of Hydroxymethyl-Furfural 113

3.5.3 Effect of Vanillin 114

3.5.4 Effect of Acetic Acid 115

3.5.5 Effect of Catechol 116

3.6 Conclusions 116

References 117

4 Dehydration of Acetonitrile Solvent by Pervaporation through Graphene Oxide/Poly(Vinyl Alcohol) Mixed Matrix Membranes 123
Siddhartha Moulik, D.Vaishnavi and S.Sridhar

4.1 Introduction 124

4.2 Materials and Methods 126

4.2.1 Materials 126

4.2.2 Preparation of Graphene Oxide 126

4.2.3 Fabrication of GO Membrane 127

4.2.4 Structural Characterization of GO/PVA Mixed Matrix Membrane 127

4.2.5 Pervaporation Experiments 127

4.2.6 Determination of Diffusion Coefficients 129

4.2.7 Membrane Characterization 130

4.2.8 Hydrodynamic Simulation 130

4.2.8.1 Specification of Computational Domain and Governing Equations 130

4.3 Results and Discussions 132

4.3.1 Scanning Electron Microscope 132

4.3.2 Differential Scanning Calorimeter 132

4.3.3 Effect of GO concentration on PV Performance 134

4.3.4 Sorption Behavior 135

4.3.5 Concentration Distribution of Water within the Membrane 135

4.3.6 Effect of Feed Water Concentration 137

4.3.7 Effect of Permeate Pressure 137

4.4 Conclusions 139

References 139

5 Recovery of Acetic Acid from Vinegar Wastewater Using Pervaporation in a Pilot Plant 141
Haresh K Dave and Kaushik Nath

5.1 Introduction 142

5.2 Materials and Methods 144

5.2.1 Chemicals and Membranes 144

5.2.2 Preparation and Cross-Linking of Membrane 144

5.2.3 Equilibrium Sorption in PVA-PES Membrane 144

5.2.4 Permeation Experimental Study 145

5.2.5 Flux and Separation Factor 146

5.2.6 Permeability and Membrane Selectivity 147

5.2.7 Diffusion and Partition Coefficient 147

5.2.8 Thermogravimetric Analysis 148

5.2.9 FTIR Analysis 148

5.2.10 AFM and SEM Analysis 148

5.2.11 Mechanical Properties 149

5.3 Results and Discussion 149

5.3.1 Sorption in PVA-PES Membrane 149

5.3.2 Effect of Feed Composition on Flux and Separation Factor 151

5.3.3 Activation Energy and Heat of Sorption 152

5.3.4 Permeability, Permeance and Intrinsic Membrane Selectivity 153

5.3.5 Diffusion and Partition Coefficient 154

5.3.6 Thermogravimetric Analysis 156

5.3.7 Surface Chemistry by FTIR Analysis 156

5.3.8 Surface Topology by AFM Analysis 159

5.3.9 Surface Topology by SEM Analysis 161

5.3.10 Mechanical Properties of the Membrane 162

5.3.11 Reusability of the Membrane 163

5.4 Conclusion 164

Nomenclature 165

Acknowledgement 165

References 166

6 Thermodynamic Models for Prediction of Sorption Behavior in Pervaporation 169
Reddi Kamesh, Sumana Chenna and K. Yamuna Rani

6.1 Introduction 170

6.2 Thermodynamic Models for Sorption 172

6.2.1 Flory-Huggins Models 172

6.2.1.1 Models for Single Liquid Sorption in Polymer 172

6.2.1.2 Models for Binary Liquid Sorption in Polymer 175

6.2.2 UNIQUAC Model 180

6.2.2.1 Calculation of Binary Solvent-Solvent Interaction Parameters (τij & τji) 181

6.2.2.2 Calculation of Binary Polymer-Solvent Interaction Parameters (τim, τmi & τjm, τmj) 184

6.2.2.3 Prediction of Sorption Levels for a Ternary System Using UNIQUAC Model 185

6.2.3 UNIQUAC-HB Model 187

6.2.3.1 Calculation of Binary Solvent-Solvent Interaction Parameters (τʹij and τʹji ) 187

6.2.3.2 Calculation of Binary Solvent-Polymer Interaction Parameters 188

6.2.3.3 Prediction of Sorption Levels for a Ternary System 189

6.2.4 Modified NRTL Model 190

6.2.4.1 Calculation of Binary Solvent-Solvent Interaction Parameters (τ12 & τ21) 192

6.2.4.2 Calculation of Binary Polymer-Solvent Interaction Parameters (τiM & τMi) 192

6.2.4.3 Prediction of Sorption Behavior for a Ternary System - Method 1 193

6.2.4.4 Prediction of Sorption Behavior for a Ternary System - Method 2 194

6.3 Computational Procedure 196

6.4 Case Study 202

6.5 Summary and Conclusions 207

References 208

7 Molecular Dynamics Simulation for Prediction of Structure-Property Relationships of Pervaporation Membranes 211
Shaik Nazia, Siddhartha Moulik, Jega Jegatheesan, Suresh K. Bhargava and S. Sridhar

7.1 Introduction and Historical Perspective 212

7.2 Molecular Dynamics (MD) Simulations 213

7.3 Calculation of Interaction Parameters 214

7.4 Calculation of Permeation Properties 216

7.5 Free Volume Analysis 220

7.6 Conclusions 224

References 224

8 Vapor Permeation: Fundamentals, Principles and Applications 227
Siddhartha Moulik, Sowmya Parakala and S. Sridhar

8.1 Introduction and Historical Perspective 228

8.2 Principle 229

8.3 Mass Transfer Models in Vapor Permeation 231

8.4 Membranes for VP 233

8.4.1 Inorganic Membranes 233

8.4.2 Polymeric Membranes: 236

8.4.3 Mixed Matrix Membranes (MMMs) 239

8.5 Applications of Vapor Permeation 243

8.6 Conclusions and Future Trends 252

References 252

9 Vapor Permeation - A Thermodynamic Perspective 257
Sujay Chattopadhyay

9.1 Introduction 258

9.2 Parameters Influencing Vapor Permeation 259

9.3 Sorption in Polymeric Materials 262

9.3.1 Sorption of Pure Liquid or Vapors 263

9.3.2 Sorption of Binary Mixtures of Liquids and Vapors 264

9.4 Vapor Permeation in Polymeric Membranes 265

9.4.1 Vapor Permeation Through Rubbery Membranes 265

9.4.2 Vapor Permeation Through Glassy Membranes 265

9.4.3 Vapor Permeation Through Crystalline Polymers 267

9.5 Thermodynamics of Penetrant/Polymer Membrane 268

9.6 Non-Equilibrium Thermodynamics 271

9.7 Design of Vapor Permeation Membrane with High Selectivity 273

9.8 Membranes and Membrane Modules 276

9.9 Applications of Vapor Permeation 277

9.10 Conclusion 279

References 280

10 Vapor Permeation: Theory and Modelling Perspectives 283
Harsha Nagar, P. Anand and S. Sridhar

10.1 Introduction 284

10.2 Advantages of Vapor Permeation Process 287

10.3 Mass Transfer Mechanism in VP Process 287

10.4 Fundamentals of Vapor Permeation Modelling 288

10.4.1 Solution-Diffusion Mechanisms 289

10.4.2 Diffusion Modelling 290

10.4.2.1 Multi-Component Diffusion 292

10.4.3 Solubility Modelling 293

10.4.3.1 Equation of State Approach 293

10.4.3.2 Lattice Fluid-Based Models 294

10.5 Case Studies of VP Modelling 296

10.5.1 Modelling of a Multi-Component System for Vapor Permeation Process 296

10.5.2 Cost Effective Vapor Permeation Process for Isopropanol Dehydration 298

10.5.3 Vapor Permeation Modeling for Inorganic Shell and Tube Membranes. 299

10.6 Conclusion 301

References 302

11 Membrane Distillation: Historical Perspective and a Solution to Existing Issues of Membrane Technology 305
Siddhartha Moulik, Sowmya Parakala and S. Sridhar

11.1 Introduction and Historical Perspective of Membrane Distillation 306

11.2 Principle of Membrane Distillation 308

11.3 Mass Transfer in MD 312

11.4 Parameters Affecting Performance of MD 314

11.5 Heat Transfer in MD 317

11.6 Membranes for MD 318

11.7 Applications of Membrane Distillation 328

11.7.1 Seawater Desalination 328

11.7.2 Drinking Water Purification 333

11.7.3 Oily Wastewater Treatment 338

11.7.4 Solvent Dehydration 340

11.7.5 Treatment of Textile Industrial Effluent 343

11.7.6 Food Industrial Applications 345

11.7.7 Treatment of Radioactive Waste Water 346

11.7.8 Dairy Effluent Treatment 347

11.8 Conclusions and Future Trends 350

References 351

12 Dewatering of Diethylene Glycol and Lactic Acid Solvents by Membrane Distillation Technique 357
M. Madhumala, I. Ravi Kiran, Shakarachar M. Sutar and S. Sridhar

12.1 Introduction 358

12.2 Materials and Methods 360

12.2.1 Materials 360

12.2.2 Membrane Synthesis 360

12.2.2.1 Synthesis of Microporous Hydrophobic ZSM-5/PVC Mixed Matrix Membrane 360

12.2.2.2 Synthesis of Ultraporous Hydrophobic Polyvinylchloride Membrane 361

12.2.3 Experimental 361

12.2.3.1 Description of Membrane Distillation Set-up 361

12.2.3.2 Experimental Procedure 362

12.2.4 Membrane Characterization Techniques 363

12.2.4.1 Fourier Transform Infrared Spectroscopy (FT-IR) 363

12.2.4.2 X-Ray Diffraction Studies (XRD) 363

12.2.4.3 Thermo Gravimetric Analysis (TGA) 364

12.2.4.4 Scanning Electron Microscopy (SEM) 364

12.2.4.5 Contact Angle Measurement 364

12.3 Results and Discussion 364

12.3.1 Membrane Characterization 364

12.3.1.1 FTIR 364

12.3.1.2 XRD 366

12.3.1.3 TGA 367

12.3.1.4 SEM 368

12.3.1.5 Contact Angle Measurement 369

12.3.2 Case Study 1: Dehydration of Lactic Acid Using ZSM-5 Loaded Polyvinyl Chloride Membrane 369

12.3.2.1 Effect of Feed Lactic Acid Concentration on Membrane Performance 369

12.3.3 Case Study 2: Dehydration of Diethylene Glycol Using Ultraporous PVC Membrane 371

12.3.3.1 Effect of Feed Diethylene Glycol Concentration on Membrane Performance 371

12.4 Conclusions 372

References 373

13 Graphene Oxide/Polystyrene Mixed Matrix Membranes for Desalination of Seawater through Vacuum Membrane Distillation 375
Siddhartha Moulik, Sowmya Parakala and S. Sridhar

13.1 Introduction 376

13.1.1 Graphene and its Derivatives 378

13.2 Materials and Methods 380

13.2.1 Materials 380

13.2.2 Preparation of Graphene Oxide 380

13.2.3 Membrane Synthesis 381

13.2.4 Performance of the Crosslinked GO Loaded PS Membrane 382

13.2.5 Membrane Distillation Experiment 383

13.2.6 Membrane Characterization 384

13.2.7 Computational Fluid Dynamics Study 384

13.2.7.1 Model Development 384

13.3 Results and Discussions 388

13.3.1 Membrane Characterization 388

13.3.1.1 SEM 388

13.3.1.2 Contact Angle Measurement 389

13.3.1.3 FTIR 390

13.3.1.4 Raman Spectra 391

13.3.2 Effect of GO Concentration on MD Performance 391

13.3.3 Concentration Profile of Water Vapor within the Membrane 392

13.3.4 Effect of Feed Salt Concentration 393

13.3.5 Effect of Degree of Vacuum on MD Performance 395

13.3.6 Effect of Membrane Thickness 395

13.4 Conclusion 396

References 397

14 Vacuum Membrane Distillation for Water Desalination 399
Sushant Upadhyaya, Kailash Singh, S.P. Chaurasia, Rakesh Baghel and Sarita Kalla

14.1 Introduction 400

14.2 Membrane Distillation 400

14.2.1 Direct Contact Membrane Distillation (DCMD) 400

14.2.2 Air Gap Membrane Distillation (AGMD) 401

14.2.3 Sweeping Gas Membrane Distillation (SGMD) 401

14.2.4 Vacuum Membrane Distillation (VMD) 401

14.3 Selection Criteria for MD Membrane 402

14.4 Characterization of Membranes in MD 403

14.5 Applications 403

14.6 Modelling in MD 404

14.7 Mass and Heat Transport in VMD 407

14.8 Recovery Modelling in VMD 410

14.9 Operating Variables Influence on VMD Process 411

14.9.1 Variation in Permeate Flux with Feed Rate 411

14.9.2 Variation in Permeate Flux with Feed Inlet Temperature 412

14.9.3 Variation in Permeate Flux with Permeate Pressure 415

14.9.4 Variation in Permeate Flux with Feed Salt Concentration 416

14.9.5 Effect of Runtime 417

14.10 Water Recovery 418

14.11 Fouling on Membrane 420

14.12 Conclusions 424

Nomenclature 425

Greek Symbols 426

References 426

15 Glycerol Purification Using Membrane Technology 431
Priya Pal, S.P.Chaurasia, Sushant Upadhyaya, Madhu Agarwal and S. Sridhar

15.1 Introduction 432

15.2 Glycerol 433

15.2.1 Impurities Present in Crude Glycerol 433

15.3 Sources of Glycerol 434

15.3.1 Transesterification Reaction 435

15.3.2 Saponification of Oils and Fats 436

15.3.3 Hydrolysis of Oils and Fats 436

15.4 Purification Processes 440

15.4.1 Conventional Method (Physicochemical Method) 440

15.4.1.1 Pre-Treatment (Acidification and Neutralization) 440

15.4.1.2 Solvent Removal 441

15.4.1.3 Activated Charcoal Treatment for Color Removal 442

15.4.1.4 Ion-Exchange Adsorption 442

15.4.2 Membrane Technology 443

15.4.2.1 Membrane Distillation (MD) 443

15.4.2.2 Operating Variables Affecting VMD Process 447

15.5 Material and Methods 453

15.5.1 Materials 453

15.5.2 Synthesis of Hydrophobic Polyvinylidene Fluoride (PVDF) Membrane 453

15.5.3 Methods 453

15.5.4 Membrane Characterization 455

15.5.4.1 Scanning Electron Microscopy (SEM) 455

15.5.4.2 Membrane Porosity Measurement 455

15.5.4.3 Membrane Thickness 456

15.5.4.4 Contact Angle 456

15.5.4.5 FTIR 457

15.6 Results and Discussion 457

15.6.1 Characterization of Membrane 457

15.6.2 Effect of Glycerol Concentration on Flux and Percentage Rejection 459

15.7 Conclusions 459

Nomenclature 460

References 461

16 Reclamation of Water and Toluene from Bulk Drug Industrial Effluent by Vacuum Membrane Distillation 467
Pavani Vadthya, Y.V.L. Ravikumar and S. Sridhar

16.1 Introduction 468

16.2 Materials and Methods 469

16.2.1 Materials 469

16.2.2 Membrane Synthesis 469

16.2.3 Membrane Characterization 470

16.2.3.1 Fourier-Transform Infrared Spectroscopy (FTIR) 470

16.2.3.2 Scanning Electron Microscopy (SEM) 470

16.2.3.3 X-Ray Diffraction Studies (XRD) 470

16.2.3.4 Sorption Studies 470

16.2.4 Experimental Set Up 471

16.2.5 Experimental Procedure 471

16.2.6 Flux 471

16.2.7 Refractive Index 472

16.3 Results and Discussion 472

16.3.1 Membrane Characterization 472

16.3.1.1 FTIR 472

16.3.1.2 SEM 473

16.3.1.3 XRD 473

16.3.1.4 Sorption Studies 474

16.3.2 Effect of Membrane Thickness 476

16.3.3 Effect of Polymer Loading 476

16.3.4 Effect of Permeate Pressure 477

16.4 Conclusions 479

References 480

Index 481

Authors

S. Sridhar Siddhartha Moulik