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

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. This outstanding new volume: Covers advanced membrane processes for intricate separations involved in industries and other societal relevant problems such as separation of azeotropic mixtures, close-boiling compounds, organic–organic liquid mixtures, effluent treatment, and seawater desalinationProvides fundamental applications of computational fluid dynamics (CFD) and molecular dynamics (MD) simulation to scale up processes to a commercial levelNot only illustrates and cites problems and solutions, but also thoroughly covers membrane engineering, including timely and suitably placed theoretical analyses of membrane-based separationsTargets a wider audience from graduate students to membrane researchers covering the potential of membrane processes for solving challenging separation problems including students and teachers in the field of chemical engineering and effluent treatment, researchers in the field of effluent treatment and resource, process engineers, and plant managers in various industries