Membrane Processes

Dr. Sundergopal Sridhar, PhD. is a chemical engineer from the University College of Technology, Osmania University, Hyderabad. He has been working as a scientist in the area of membrane separation processes at the Indian Institute of Chemical Technology in Hyderabad for the past 20 years and has published over 130 research papers and is the recipient of 30 prestigious scientific awards. Siddhartha Moulik is a scientist at the Indian Institute of Chemical Technology in Hyderabad. He has published 16 research papers in various international journals, 2 book chapters, and 39 papers in conference proceedings. He is also the recipient of 8 prestigious awards in his field.

• Preface xvii1 Tackling Challenging Industrial Separation Problems through Membrane Processes 1Siddhartha Moulik, Sowmya Parakala and S. Sridhar1.1 Water: The Source of Life 21.2 Significance of Water/Wastewater Treatment 51.3 Wastewater Treatment Techniques 81.4 Membrane Technologies for Water/Wastewater Treatment 111.5 Membranes: Materials, Classification and Configurations 121.5.1 Types of Membranes 121.5.1.1 Symmetric Membranes 121.5.1.2 Asymmetric Membranes 131.5.1.3 Electrically Charged Membranes 141.5.1.4 Inorganic Membranes 141.5.2 Membranes Modules and Their Characteristics 141.6 Introduction to Membrane Processes 171.6.1 Conventional Membrane Processes 171.7 CSIR-IICT’s Contribution for Water/Wastewater Treatment 211.7.1 Nanofiltration Plant for Processing Coke Oven Wastewater in Steel Industry 221.8 Potential of Pervaporation (PV), Vapor Permeation (VP), and Membrane Distillation (MD) in Wastewater Treatment 241.9 Conclusion 32References 332 Pervaporation Membrane Separation: Fundamentals and Applications 37Siddhartha Moulik, Bukke Vani, D. Vaishnavi and S. Sridhar2.1 Introduction and Historical Perspective 382.2 Principle 402.2.1 Mass Transfer 422.2.2 Factors Affecting Membrane Performance 442.3 Membranes for Pervaporation 452.4 Applications of Pervaporation 462.4.1 Solvent Dehydration 462.4.2 Organophilic Separation 552.4.2.1 Removal of VOCs 572.4.2.2 Extraction of Aroma Compounds 582.4.3 Organic/Organic Separation 642.4.3.1 Separation of Polar/Non-Polar Mixture 642.4.3.2 Separation of Aromatic/Alicyclic Mixtures 702.4.3.3 Separation of Aromatic/Aliphatic/Aromatic Hydrocarbons 712.4.3.4 Separation of Isomers 722.5 Conclusions and Future Prospects 77References 783 Pervaporation for Ethanol-Water Separation and Effect of Fermentation Inhibitors 89Anjali Jain, Sushant Upadhyaya, Ajay K. Dalai and Satyendra P. Chaurasia3.1 Introduction 903.2 Theory of Pervaporation 913.2.1 Applications of Pervaporation 923.2.2 Advantages of Pervaporation 933.2.3 Pervaporation Performance Evaluation Parameters 933.3 Various Membranes Used for the Recovery of Ethanol 943.3.1 Organic Membranes 943.3.2 Inorganic Membranes 1023.3.3 Mixed Matrix Membranes 1043.4 Effects of Process Variables on Ethanol Concentration in PV 1063.4.1 Effect of Feed Flow Rate 1063.4.2 Effect of Ethanol Concentration in Feed 1073.4.3 Effect of Feed Temperature 1083.4.4 Effect of Permeate Pressure 1093.5 Effect of Fermentation Inhibitors on Pervaporation Performance 1093.5.1 Effect of Furfural Concentration 1123.5.2 Influence of Hydroxymethyl-Furfural 1133.5.3 Effect of Vanillin 1143.5.4 Effect of Acetic Acid 1153.5.5 Effect of Catechol 1163.6 Conclusions 116References 1174 Dehydration of Acetonitrile Solvent by Pervaporation through Graphene Oxide/Poly(Vinyl Alcohol) Mixed Matrix Membranes 123Siddhartha Moulik, D.Vaishnavi and S.Sridhar4.1 Introduction 1244.2 Materials and Methods 1264.2.1 Materials 1264.2.2 Preparation of Graphene Oxide 1264.2.3 Fabrication of GO Membrane 1274.2.4 Structural Characterization of GO/PVA Mixed Matrix Membrane 1274.2.5 Pervaporation Experiments 1274.2.6 Determination of Diffusion Coefficients 1294.2.7 Membrane Characterization 1304.2.8 Hydrodynamic Simulation 1304.2.8.1 Specification of Computational Domain and Governing Equations 1304.3 Results and Discussions 1324.3.1 Scanning Electron Microscope 1324.3.2 Differential Scanning Calorimeter 1324.3.3 Effect of GO concentration on PV Performance 1344.3.4 Sorption Behavior 1354.3.5 Concentration Distribution of Water within the Membrane 1354.3.6 Effect of Feed Water Concentration 1374.3.7 Effect of Permeate Pressure 1374.4 Conclusions 139References 1395 Recovery of Acetic Acid from Vinegar Wastewater Using Pervaporation in a Pilot Plant 141Haresh K Dave and Kaushik Nath5.1 Introduction 1425.2 Materials and Methods 1445.2.1 Chemicals and Membranes 1445.2.2 Preparation and Cross-Linking of Membrane 1445.2.3 Equilibrium Sorption in PVA-PES Membrane 1445.2.4 Permeation Experimental Study 1455.2.5 Flux and Separation Factor 1465.2.6 Permeability and Membrane Selectivity 1475.2.7 Diffusion and Partition Coefficient 1475.2.8 Thermogravimetric Analysis 1485.2.9 FTIR Analysis 1485.2.10 AFM and SEM Analysis 1485.2.11 Mechanical Properties 1495.3 Results and Discussion 1495.3.1 Sorption in PVA-PES Membrane 1495.3.2 Effect of Feed Composition on Flux and Separation Factor 1515.3.3 Activation Energy and Heat of Sorption 1525.3.4 Permeability, Permeance and Intrinsic Membrane Selectivity 1535.3.5 Diffusion and Partition Coefficient 1545.3.6 Thermogravimetric Analysis 1565.3.7 Surface Chemistry by FTIR Analysis 1565.3.8 Surface Topology by AFM Analysis 1595.3.9 Surface Topology by SEM Analysis 1615.3.10 Mechanical Properties of the Membrane 1625.3.11 Reusability of the Membrane 1635.4 Conclusion 164Nomenclature 165Acknowledgement 165References 1666 Thermodynamic Models for Prediction of Sorption Behavior in Pervaporation 169Reddi Kamesh, Sumana Chenna and K. Yamuna Rani6.1 Introduction 1706.2 Thermodynamic Models for Sorption 1726.2.1 Flory-Huggins Models 1726.2.1.1 Models for Single Liquid Sorption in Polymer 1726.2.1.2 Models for Binary Liquid Sorption in Polymer 1756.2.2 UNIQUAC Model 1806.2.2.1 Calculation of Binary Solvent-Solvent Interaction Parameters (τij & τji) 1816.2.2.2 Calculation of Binary Polymer-Solvent Interaction Parameters (τim, τmi & τjm, τmj) 1846.2.2.3 Prediction of Sorption Levels for a Ternary System Using UNIQUAC Model 1856.2.3 UNIQUAC-HB Model 1876.2.3.1 Calculation of Binary Solvent-Solvent Interaction Parameters (τʹij and τʹji ) 1876.2.3.2 Calculation of Binary Solvent-Polymer Interaction Parameters 1886.2.3.3 Prediction of Sorption Levels for a Ternary System 1896.2.4 Modified NRTL Model 1906.2.4.1 Calculation of Binary Solvent-Solvent Interaction Parameters (τ12 & τ21) 1926.2.4.2 Calculation of Binary Polymer-Solvent Interaction Parameters (τiM & τMi) 1926.2.4.3 Prediction of Sorption Behavior for a Ternary System – Method 1 1936.2.4.4 Prediction of Sorption Behavior for a Ternary System – Method 2 1946.3 Computational Procedure 1966.4 Case Study 2026.5 Summary and Conclusions 207References 2087 Molecular Dynamics Simulation for Prediction of Structure-Property Relationships of Pervaporation Membranes 211Shaik Nazia, Siddhartha Moulik, Jega Jegatheesan, Suresh K. Bhargava and S. Sridhar7.1 Introduction and Historical Perspective 2127.2 Molecular Dynamics (MD) Simulations 2137.3 Calculation of Interaction Parameters 2147.4 Calculation of Permeation Properties 2167.5 Free Volume Analysis 2207.6 Conclusions 224References 2248 Vapor Permeation: Fundamentals, Principles and Applications 227Siddhartha Moulik, Sowmya Parakala and S. Sridhar8.1 Introduction and Historical Perspective 2288.2 Principle 2298.3 Mass Transfer Models in Vapor Permeation 2318.4 Membranes for VP 2338.4.1 Inorganic Membranes 2338.4.2 Polymeric Membranes: 2368.4.3 Mixed Matrix Membranes (MMMs) 2398.5 Applications of Vapor Permeation 2438.6 Conclusions and Future Trends 252References 2529 Vapor Permeation - A Thermodynamic Perspective 257Sujay Chattopadhyay9.1 Introduction 2589.2 Parameters Influencing Vapor Permeation 2599.3 Sorption in Polymeric Materials 2629.3.1 Sorption of Pure Liquid or Vapors 2639.3.2 Sorption of Binary Mixtures of Liquids and Vapors 2649.4 Vapor Permeation in Polymeric Membranes 2659.4.1 Vapor Permeation Through Rubbery Membranes 2659.4.2 Vapor Permeation Through Glassy Membranes 2659.4.3 Vapor Permeation Through Crystalline Polymers 2679.5 Thermodynamics of Penetrant/Polymer Membrane 2689.6 Non-Equilibrium Thermodynamics 2719.7 Design of Vapor Permeation Membrane with High Selectivity 2739.8 Membranes and Membrane Modules 2769.9 Applications of Vapor Permeation 2779.10 Conclusion 279References 28010 Vapor Permeation: Theory and Modelling Perspectives 283Harsha Nagar, P. Anand and S. Sridhar10.1 Introduction 28410.2 Advantages of Vapor Permeation Process 28710.3 Mass Transfer Mechanism in VP Process 28710.4 Fundamentals of Vapor Permeation Modelling 28810.4.1 Solution-Diffusion Mechanisms 28910.4.2 Diffusion Modelling 29010.4.2.1 Multi-Component Diffusion 29210.4.3 Solubility Modelling 29310.4.3.1 Equation of State Approach 29310.4.3.2 Lattice Fluid-Based Models 29410.5 Case Studies of VP Modelling 29610.5.1 Modelling of a Multi-Component System for Vapor Permeation Process 29610.5.2 Cost Effective Vapor Permeation Process for Isopropanol Dehydration 29810.5.3 Vapor Permeation Modeling for Inorganic Shell and Tube Membranes. 29910.6 Conclusion 301References 30211 Membrane Distillation: Historical Perspective and a Solution to Existing Issues of Membrane Technology 305Siddhartha Moulik, Sowmya Parakala and S. Sridhar11.1 Introduction and Historical Perspective of Membrane Distillation 30611.2 Principle of Membrane Distillation 30811.3 Mass Transfer in MD 31211.4 Parameters Affecting Performance of MD 31411.5 Heat Transfer in MD 31711.6 Membranes for MD 31811.7 Applications of Membrane Distillation 32811.7.1 Seawater Desalination 32811.7.2 Drinking Water Purification 33311.7.3 Oily Wastewater Treatment 33811.7.4 Solvent Dehydration 34011.7.5 Treatment of Textile Industrial Effluent 34311.7.6 Food Industrial Applications 34511.7.7 Treatment of Radioactive Waste Water 34611.7.8 Dairy Effluent Treatment 34711.8 Conclusions and Future Trends 350References 35112 Dewatering of Diethylene Glycol and Lactic Acid Solvents by Membrane Distillation Technique 357M. Madhumala, I. Ravi Kiran, Shakarachar M. Sutar and S. Sridhar12.1 Introduction 35812.2 Materials and Methods 36012.2.1 Materials 36012.2.2 Membrane Synthesis 36012.2.2.1 Synthesis of Microporous Hydrophobic ZSM-5/PVC Mixed Matrix Membrane 36012.2.2.2 Synthesis of Ultraporous Hydrophobic Polyvinylchloride Membrane 36112.2.3 Experimental 36112.2.3.1 Description of Membrane Distillation Set-up 36112.2.3.2 Experimental Procedure 36212.2.4 Membrane Characterization Techniques 36312.2.4.1 Fourier Transform Infrared Spectroscopy (FT-IR) 36312.2.4.2 X-Ray Diffraction Studies (XRD) 36312.2.4.3 Thermo Gravimetric Analysis (TGA) 36412.2.4.4 Scanning Electron Microscopy (SEM) 36412.2.4.5 Contact Angle Measurement 36412.3 Results and Discussion 36412.3.1 Membrane Characterization 36412.3.1.1 FTIR 36412.3.1.2 XRD 36612.3.1.3 TGA 36712.3.1.4 SEM 36812.3.1.5 Contact Angle Measurement 36912.3.2 Case Study 1: Dehydration of Lactic Acid Using ZSM-5 Loaded Polyvinyl Chloride Membrane 36912.3.2.1 Effect of Feed Lactic Acid Concentration on Membrane Performance 36912.3.3 Case Study 2: Dehydration of Diethylene Glycol Using Ultraporous PVC Membrane 37112.3.3.1 Effect of Feed Diethylene Glycol Concentration on Membrane Performance 37112.4 Conclusions 372References 37313 Graphene Oxide/Polystyrene Mixed Matrix Membranes for Desalination of Seawater through Vacuum Membrane Distillation 375Siddhartha Moulik, Sowmya Parakala and S. Sridhar13.1 Introduction 37613.1.1 Graphene and its Derivatives 37813.2 Materials and Methods 38013.2.1 Materials 38013.2.2 Preparation of Graphene Oxide 38013.2.3 Membrane Synthesis 38113.2.4 Performance of the Crosslinked GO Loaded PS Membrane 38213.2.5 Membrane Distillation Experiment 38313.2.6 Membrane Characterization 38413.2.7 Computational Fluid Dynamics Study 38413.2.7.1 Model Development 38413.3 Results and Discussions 38813.3.1 Membrane Characterization 38813.3.1.1 SEM 38813.3.1.2 Contact Angle Measurement 38913.3.1.3 FTIR 39013.3.1.4 Raman Spectra 39113.3.2 Effect of GO Concentration on MD Performance 39113.3.3 Concentration Profile of Water Vapor within the Membrane 39213.3.4 Effect of Feed Salt Concentration 39313.3.5 Effect of Degree of Vacuum on MD Performance 39513.3.6 Effect of Membrane Thickness 39513.4 Conclusion 396References 39714 Vacuum Membrane Distillation for Water Desalination 399Sushant Upadhyaya, Kailash Singh, S.P. Chaurasia, Rakesh Baghel and Sarita Kalla14.1 Introduction 40014.2 Membrane Distillation 40014.2.1 Direct Contact Membrane Distillation (DCMD) 40014.2.2 Air Gap Membrane Distillation (AGMD) 40114.2.3 Sweeping Gas Membrane Distillation (SGMD) 40114.2.4 Vacuum Membrane Distillation (VMD) 40114.3 Selection Criteria for MD Membrane 40214.4 Characterization of Membranes in MD 40314.5 Applications 40314.6 Modelling in MD 40414.7 Mass and Heat Transport in VMD 40714.8 Recovery Modelling in VMD 41014.9 Operating Variables Influence on VMD Process 41114.9.1 Variation in Permeate Flux with Feed Rate 41114.9.2 Variation in Permeate Flux with Feed Inlet Temperature 41214.9.3 Variation in Permeate Flux with Permeate Pressure 41514.9.4 Variation in Permeate Flux with Feed Salt Concentration 41614.9.5 Effect of Runtime 41714.10 Water Recovery 41814.11 Fouling on Membrane 42014.12 Conclusions 424Nomenclature 425Greek Symbols 426References 42615 Glycerol Purification Using Membrane Technology 431Priya Pal, S.P.Chaurasia, Sushant Upadhyaya, Madhu Agarwal and S. Sridhar15.1 Introduction 43215.2 Glycerol 43315.2.1 Impurities Present in Crude Glycerol 43315.3 Sources of Glycerol 43415.3.1 Transesterification Reaction 43515.3.2 Saponification of Oils and Fats 43615.3.3 Hydrolysis of Oils and Fats 43615.4 Purification Processes 44015.4.1 Conventional Method (Physicochemical Method) 44015.4.1.1 Pre-Treatment (Acidification and Neutralization) 44015.4.1.2 Solvent Removal 44115.4.1.3 Activated Charcoal Treatment for Color Removal 44215.4.1.4 Ion-Exchange Adsorption 44215.4.2 Membrane Technology 44315.4.2.1 Membrane Distillation (MD) 44315.4.2.2 Operating Variables Affecting VMD Process 44715.5 Material and Methods 45315.5.1 Materials 45315.5.2 Synthesis of Hydrophobic Polyvinylidene Fluoride (PVDF) Membrane 45315.5.3 Methods 45315.5.4 Membrane Characterization 45515.5.4.1 Scanning Electron Microscopy (SEM) 45515.5.4.2 Membrane Porosity Measurement 45515.5.4.3 Membrane Thickness 45615.5.4.4 Contact Angle 45615.5.4.5 FTIR 45715.6 Results and Discussion 45715.6.1 Characterization of Membrane 45715.6.2 Effect of Glycerol Concentration on Flux and Percentage Rejection 45915.7 Conclusions 459Nomenclature 460References 46116 Reclamation of Water and Toluene from Bulk Drug Industrial Effluent by Vacuum Membrane Distillation 467Pavani Vadthya, Y.V.L. Ravikumar and S. Sridhar16.1 Introduction 46816.2 Materials and Methods 46916.2.1 Materials 46916.2.2 Membrane Synthesis 46916.2.3 Membrane Characterization 47016.2.3.1 Fourier-Transform Infrared Spectroscopy (FTIR) 47016.2.3.2 Scanning Electron Microscopy (SEM) 47016.2.3.3 X-Ray Diffraction Studies (XRD) 47016.2.3.4 Sorption Studies 47016.2.4 Experimental Set Up 47116.2.5 Experimental Procedure 47116.2.6 Flux 47116.2.7 Refractive Index 47216.3 Results and Discussion 47216.3.1 Membrane Characterization 47216.3.1.1 FTIR 47216.3.1.2 SEM 47316.3.1.3 XRD 47316.3.1.4 Sorption Studies 47416.3.2 Effect of Membrane Thickness 47616.3.3 Effect of Polymer Loading 47616.3.4 Effect of Permeate Pressure 47716.4 Conclusions 479References 480Index 481