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Desalination by Salt Replacement and Ultrafiltration

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Desalination by Salt Replacement and Ultrafiltration Desalination by salt replacement and ultrafiltration. Item Type Thesis-Reproduction (electronic); text Authors Muller, Anthony B. Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 06/10/2021 02:24:08 Link to Item http://hdl.handle.net/10150/191593 DESALINATION BY SALT REPLACEMENT AND ULTRAFILTRATION by Anthony Barton Muller A Thesis Submitted to the Faculty of the DEPARTMENT OF HYDROLOGY AND WATER RESOURCES In Partial Fulfillment of the Requirements For the Degree of MASTER OF SCIENCE WITH A MAJOR IN HYDROLOGY In the Graduate College THE UNIVERSITY OF ARIZONA 1974 STATEMENT BY AUTHOR This thesis has been submitted in partial fulfillment of require- ments for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this thesis are allowable without special permission, provided that accurate acknowledgment of source is made. Request for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGN: APPROVAL BY THESIS DIRECTOR This thesis has been approved on the date shown below: D. D. EVANS Date Professor and Head of Hydrology & Water Resources; and Professor of Soils, Water & Engineering ACKNOWLEDGMENTS The author wishes to thank Dr. Daniel D. Evans, Head of the Department of Hydrology and Water Resources, for advice and guidance in both the undergraduate and graduate programs which have led to this thesis. My thanks also go to Dr. Simon Ince and Dr. Eugene S. Simpson of the Department of Hydrology and Water Resources for serving on my thesis committee. In addition, further thanks are due to Dr. Cornelius Stellink and Dr. Leslie S. Forester of the Department of Chemistry for their patient assistance with the organic chemistry involved, and to Dr. William R. Salzman and Dr. Roald K. Wangsness of the Departments of Chemistry and Physics, respectively, for reviewing the physical chemistry and thermodynamics presented. Dr. Hasan K. Qashu of the Department of Hydrology and Water Resources, my mentor for many years, deserves great credit for helping provide the scholarly atmosphere from which this thesis has come, as does Dr. A. Richard Kassander, Vice President for Research, for providing the financial aid which allowed all aspects of this thesis to be realized. TABLE OF CONTENTS Page LIST OF TABLES vi LIST OF ILLUSTRATIONS vii ABSTRACT ix INTRODUCTION 1 Major Traditional Desalination Methods Having Received Attention as Potential Large-Scale Fresh Water Sources 5 Distillation Methods 5 Crystallization (Freezing) Methods 9 Solvent Extraction Methods 12 Chemical Separation Methods 14 Membrane Separation Methods 16 Salt Replacement: A New Method of Low-Energy Desalination Proposed for the Large-Scale Production of Fresh Water • • 24 Enzyme-Catalyzed Osmotic Pressure Reduction 25 Low-Pressure Step Ultrafiltration 32 THEORY 37 Development of Osmotic Pressure Relationships for a System in Membrane Equilibrium by Classical Thermodynamics 38 General Equilibrium Conditions 38 Membrane Equilibrium 40 Osmotic Pressure Equation 43 Development of Fundamental Equations of Flow Across a Semipermeable Membrane by Irreversible Thermodynamics 44 Entropy Production 44 Derivation of Entropy Change in Vector Notation 46 Development of Phenomenological Equations 48 Phenomenological Coefficients 51 Phenomenological Equations of an Osmotic System 53 Relationship of Derived and Empirical Expressions . 57 Development of First-Order Transport Equations and Corresponding Coefficients Describing Intrinsic Membrane Characteristics 58 Transformation of Uni-Component Flux Equations 58 Membrane Description by First-Order Transport Coefficients 62 Evaluation of First-Order Transport Coefficients 64 iv •• TABLE OF CONTENTS--Continued Page Permeation Models for Solute and Solvent Transport Kinetics of Diffusive and Microporous Osmotic Membranes 67 Solution-Diffusion Model 67 Pore Flow Model 73 Theoretical Treatment of Concentration-Polarization at Phase Boundaries in Membrane Separation Systems with Laminar Flow Regimes 81 Differential Equation for Solute Balance 83 Treatment of Constant and Variable Permeation Fluxes . 88 EXPERIMENTATION 91 Experimental Apparatus Used in Ultrafiltration of Sucrose in this Study 92 Ultrafiltration Experiments with Pure Water Solvent which Determine Hydraulic Permeability and Transport Mechanism . 99 Determination of Hydraulic Permeability 99 Determination of Transport Mechanism 104 Ultrafiltration Experiments with Variable Sucrose Concentrations Determining UM Series Membrane Fluxes and Separation at Operating Concentrations 107 Osmotic Pressure of Sucrose Solutions 107 Permeation Flux as a Function of Solute Concentration . 111 Membrane Rejection as a Function of Solute Concentration 115 Reduction of Experimental Sucrose Separation Data to Generate Solute Rejection Coefficient from Permiate-Retinate Concentration Relationships 121 Permiate-Retinate Concentration Relationships 122 Evaluation of the Solute Rejection Coefficient R 125 Reduction of Experimental Sucrose Separation Data to Generate Reflection and Solute Permeability Coefficients from Concentration-Polarization Relationship 129 Concentration-Polarization Along UM Series Membranes . 129 Evaluation of the Reflection Coefficient 140 Evaluation of the Solute Permeability Coefficient . 144 CONCLUSIONS 147 NOTATION 151 SELECTED BIBLIOGRAPHY 159 LIST OF TABLES Table Page 1. Principal Traditional Desalination Methods 4 2. Published UM Membrane Series Characteristics 95 3. Experimental Results and Determination of L 100 4. Comparison of Published and Observed L Values 103 S. Comparison of Pure Solvent Fluxes 105 6. Osmotic Pressure of Sucrose Solutions 109 7. Solute Reflection Coefficients 126 8. Boundary Layer Concentration 131 9. Bulk Permeation Flux Prediction 137 10. Concentration-Polarization Permeation Flux Prediction . 139 ll. Reflection Coefficients 142 12. Reflection Coefficient Adjusted Permeation Flux Prediction . 143 13. Solute Permeability Coefficient Evaluation 146 14. First-Order Transport Coefficients for UM Series Membranes . 148 vi LIST OF ILLUSTRATIONS Figure Page 1. Solute-Solvent Separation Processes Useful in Various Solute Size Ranges, and the Primary Underlying Separation Principal of Each 26 2. Salt Replacement Desalination 27 3. Desalination by Salt Replacement and Enzyme-Catalyzed Osmotic Pressure Reduction with Ultrafiltration 28 4. The Molecular Configuration of the Principal Disaccharides: Sucrose, Maltose, Cellobiose and Lactose 30 5. Concentration Profiles in a Solution-Diffusion Membrane 72 6. Angular Deformation of a Fluid Element 74 7. Laminar Flow Through a Cylindrical Tube 75 8. Concentration Profiles in Pore-Flow Membranes 80 9. Two-Dimensional Channel Between Flat Parallel Osmotic Membranes 83 10. Profile of Concentration-Polarization at Channel Boundary for Laminar Flow Along a Membrane Surface 84 11. Schematic Representation of Experimental Apparatus Used in the Ultrafiltration of Sucrose in this Study 93 12. Thin-Channel Ultrafiltration Cell 94 13. Volumetric Flux Versus Applied Pressure, Results of Pure Solvent Runs at Various Pressures Used to Determine L for the UM Series Membranes. 1 01 14. UM05 Permeation Flux Versus Sucrose Molality, in ml of Solution Per 5 Minutes from the Ultrafiltration Cell at 40 psi 113 15. UM2 Permeation Flux Versus Sucrose Molality, in ml of Solution Per 5 Minutes from the Ultrafiltration Cell at 40 Psi 114 vii vi ii LIST OF ILLUSTRATIONS--Continued Figure Page 16. UM10 Permeation Flux Versus Sucrose Molality in ml of Solution Per 5 Minutes from the Ultrafiltration Cell at 40 psi 116 17. Retinate Versus Permiate Molalities for UM05 (-), UM2 (+) and UM10 (o) Ultrafiltration Membranes -119 18. Retinate Versus Permiate Molalities for UM Series Membrane at Low Concentrations 120 19. Separation Relationship Observed by 'Kimura and Sourirajan (1968d) and Adjusted for Comparison to this Study, at Various Pressures and with Various Membranes 124 20. Membrane Performance Diagram for the UM Series Membranes, with Rejection Coefficient Plotted Against Retinate Concentrations 127 21. UM10 Permeation Flux Predictions Versus Sucrose Molality, Considering Hydraulic Permeability (o), Concentration- Polarization (+) and Reflection Coefficient (-) 133 22. UM2 Permeation Flux Predictions Versus Sucrose Molality, Considering Hydraulic Permeability (o), Concentration- Polarization (+) and Reflection Coefficient (•) 134 23. UM05 Permeation Flux Predictions Versus Sucrose Molality, Considering Hydraulic Permeability (o), Concentration- Polarization (+) and Reflection Coefficient (•) 135 ABSTRACT The replacement of solutes in a saline solution by a replacer chemical across an osmotic membrane, and the subsequent removal of the chemical by virtue of its special removal characteristics, comprises salt replacement desalination. Any of a number of removal processes may be coupled to the replacement step, the process being determined
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