NATURAL ORGANICS REMOVAL USING MEMBRANES Copyright © 2001 by Andrea I. Schafer HOW TO ORDER THIS BOOK BY PHONE: 800-233-9936 Or 71 7-291 -5609, AM- PM Eastern Time BY FM: 71 7-295-4538 BY MAIL: Order Department Technomic Publishing Company, Inc. 851 New Holland Avenue, Box 3535 Lancaster, PA 17604, U.S.A. BY CREDIT CARD: American Express, VISA, Mastercard PERMISSION TO PHOTOCOPY-POLICY STATEMENT Authorization to photocopy items for internal or personal use, or the internal or personal use of specificclients, is granted by Technomic Publishing Co., Inc. provided that the base fee of US $5.00 per copy, plus US $.25 per page is paid directly to Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, USA. For those organizations that have been granted a photocopy license by CCC, a separate system of payment has been arranged. The fee code for users of the Transactional Reporting Service is 1-58716101 $5.00 + $.25. Copyright © 2001 by Andrea I. Schafer PRINCIPLES, PERFORMANCE AND COST Andrea Iris Schafer, PhoDo Scbd of Civil and Environmtul Engineeriw University of New Soutb Wak, Australia Copyright © 2001 by Andrea I. Schafer Natural Organics Removal Using Membranes ~TECHNOMIC~U~~~C~~~O~ Technomic Publishing Company, Inc. 851 New Holland Avenue, Box 3535 Lancaster, Pennsylvania 17604 U.S.A. Copyright O 2001 by Andrea I. Schiifer All rights reserved No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher. Printed in the United States of America l0987654321 Main entry under title: Natural Organics Removal Using Membranes: Principles, Performance and Cost A Technomic Publishing Company book Bibliography: p. Includes index p. 401 Library of Congress Catalog Card No. 2001088343 ISBN NO. 1-58716-093-5 Copyright © 2001 by Andrea I. 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Schafer CONTENTS Foreword xvii Preface xix Acknowledgements xxi Chapter 1 - Introdrrction Chapter 2 - Charactetisation ofNatrrral Organics - A Review 2.1 INTRODUCTION 6 2.2 DEFINITION OF NATURAL ORGANICS 7 2.2.1 Nature of Different Natural Organics 2.2.2 Definition of Compounds 2.3 ORIGIN OF NATURAL ORGANICS 8 Chemical Formation, Humification and Xgmg Biologcal Activity Soil and Vegetation Weather and Seasonal Variations Lake Waters versus Freshwater Streams Groundwa ter Pollution by Human Activity Availability for Research 2.4 EXTRACTION OF NATURAL ORGANICS FROM WATERS 10 2.4.1 Ion Eschange Resin 2.4.2 Reverse Osmosis 2.4.3 Desalting 2.4.4 Purification 2.5 CHARACTERISATION OF NATURAL ORGANICS 13 2.5.1 Concentration Measurements of Natural Organics 2.5.2 Aromaticity and Reactivity 2.5.3 Hydrophobicity 2.5.4 Size, Molecular Weight, RadLi of Gyration, Polydispersity 2.5.5 Diffusion Coefficient 2.5.6 Elemental Analysis and Structure 2.5.7 Functional Groups vii Copyright © 2001 by Andrea I. Schafer viii Contents 2.5.8 Charge and Acidity 2.5.9 Solubhty and Aggregation of Natural Organics 2.5.10 Micelle Formation of Natural Organics and Surfactant Characteristcs 2.5.1 1 Structure/Fractal Dimension of Natural Organics 2.6 FRACTIONATION OF NATURAL ORGANICS 24 2.6.1 Particulate/Dissolved Organic Carbon Separation 2.6.2 FX/KI Separation 2.6.3 Size/hnX' Fractionation 2.6.4 Hydrophhc/Hydrophobic Fractionation 2.7 VARIATIONS OF NATURAL ORGANICS CHARACTERISTICS WITH SOLUTION CHEMISTRY 25 2.7.1 Effect of Organic Concentration 2.7.2 Effect of Ionic Strength 2.7.3 Effect of pH 2.8 INTERACTIONS OF NATURAL ORGANICS WITH OTHER SOLUTES 26 2.8.1 Cations 2.8.2 Trace Metals 2.8.3 Interactions with Other Compounds 2.9 INTERACTIONS OF NATURAL ORGANICS WITH COLLOIDS 28 2.9.1 Characterisation of Natural Organics and Colloid Systems 2.9.2 Organic Adsorption onto Colloids 2.9.3 Colloid Stabilisation and Mobilisation 2.9.4 Aggregate Formation and Structure 2.10 NATURAL ORGANICS IN WATER TREATMENT 32 2.10.1 Drinking Water Standards 2.10.2 Treatabllity of Natural Organics by Different Processes 2.10.3 Disinfection By-Product Formation 2.10.4 Bacterial Regrowth, Biofhs and Conditioning Films 2.10.5 Membrane Fouling Chapter 3 - Membrane Review 39 3.1 INTRODUCTION AND OVERVIEW 40 3.2 FUNDAMENTAL PRINCIPLES AND MECHANISMS 42 3.2.1 hficrofdtration @IF) 3.2.2 Ultrafdtration (UF) 3.2.3 Nanofdtration @F) 3.2.4 Reverse Osmosis (RO) Copyright © 2001 by Andrea I. Schafer Contents ix 3.3.1 Membrane Materials for hIF and UF 3.3.2 Membrane Materials for NF and R0 3.3.3 TFC Membrane Modification in NF 3.3.4 Membrane Selection, Testing and Evaluation 3.4 RETECTION OF NATURAL ORGANICS AND COLLOIDS 55 3.4.1 hficrofdtration (MF) 55 3.4.2 Ultrafiltration (Ul?) 55 3.4.3 Nanofdtration and Reverse Osmosis 57 3.4.4 Variation of Rejection due to Fouling 62 3.5 FOULING BY NATURAL ORGANICS AND COLLOIDS 63 3.5.1 Organic Fouling 63 3.5.2 Inorganic Fouhg or Scaling 68 3.5.3 Colloid and Particle Fouling 69 3.6 MEMBRANE AND FOULING LAYER CHARACTERISATION 75 3.6.1 Microscopic Techniques 3.6.2 Surface Charge 3.6.3 Hydrophobicity and State of Water 3.6.4 Deposit Morphology and Surface Analysis 3.7 FOULING CONTROL 78 3.7.1 Pretreatment for Rejection Increase and Fouling Prevention 3.7.2 Backwashing, Backflushing, and Operation Mode 3.7.3 Membrane Cleaning 3.8 MEMBRANE PROCESS APPLICATIONS IN WATER TREATMENT 84 3.8.1 Membrane Processes versus Conventional Treatment 3.8.2 Membranes versus other Alternatives 3.8.3 Micro filtration 3.8.4 Ultrafiltration 3.8.5 Nanofdtration and Reverse Osmosis 3.8.6 Hybrid Membrane Processes 3.8.7 Cost 3.9 CONCLUSION 89 Chapter 4 - Materials and Methods 91 4.1 CHEMICALS AND BACKGROUND SOLUTION 92 4.2 ORGANICS 92 4.3 HEMATITE COLLOIDS (a-FE70d 93 4.4 MEMBRANES 93 4.4.1 bficrofiltration Membranes 4.4.2 Ultrafdtration Membranes Copyright © 2001 by Andrea I. Schafer X Contents 1.4.3 Nanofdtration Membranes 93 4.5 FILTRATION EQUIPMENT 96 4.5.1 Micro filtration Equipment 4.5.2 Ultrafdtration Equipment 4.5.3 Nanofdtration Equipment 4.6 GENERAL ANALYTICAL METHODS 98 4.6.1 pH Value 4.6.2 Conductivity 4.6.3 Inductively Coupled Plasma L\tomic Emission Spectroscopy (ICP-L\ES) 4.6.4 Ion Chromatography (IC) 4.7 ORGANICS CHARACTERISATION 99 4.7.1 Dissolved Organic Carbon (DOC) 4.7.2 UV/VTS Spectroscopy 1.7.3 Titration 4.7.4 Elemental Analysis 4.7.5 XAD Fractionation 4.7.6 Cation Content of Organics 4.7.7 High Performance Size Exclusion Chromatography (HPLC-SEC) 4.7.8 Ultra filtration Fractionation 4.7.9 Liquid Chromatography - Organic Carbon Detection &C-OCD) 4.7.10 Humic Solubhty and Aggregation 4.7.11 Viscosity 4.7.12 Matrix Assisted Laser Desorption/Ionisation (MALDI) 4.7.13 Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFT) 4.8 SOLUTION PREPARATION 116 4.8.1 Stable Hematite Colloids in Absence of Organics 4.8.2 Colloids at pH 3 with Organics 4.8.3 Reaction Limited Aggregation @M) 4.8.4 Diffusion Limited Aggregation (DLA) 4.8.5 SPO: Aggregates with Organics 4.8.6 OPS: Colloids Stabilised with Organics 4.8.7 Coagulation 4.9 PARTICLE AND AGGREGATE CHARACTERISATION 120 4.9.1 Zeta Potential and Mobhty of Particles 4.9.2 Particle Size and Structure ;inalysis/Fractal Dimension (Malvern) 4.9.3 Aggregate Size 4.9.4 ,iggregate Structure 4.9.5 Photon Correlation Spectroscopy (PCS) 4.10 MEMBRANE AND DEPOSIT CHARACTERISATION 127 4.10.1 Zeta Potential of Membranes 4.10.2 Field Emission Scanning Electron mcroscopp (FESEhl) 4.10.3 Electron Dispersive Spectra (EDS) Copyright © 2001 by Andrea I. Schafer [...]... ANALYSIS 14 2 14 2 14 3 14 3 14 5 14 5 14 6 14 8 14 8 14 8 14 9 14 9 14 9 15 0 5.9 .1 Stable Colloids in the Absence of Organics 5.9.2 Aggregated Colloids with Subsequent Adltion of Organics (SPO) 5.9.3 Stabilised Colloids (OPS) 5 .10 MF OF FECL?-COAGULATED SOLUTIONS 15 4 5 .10 .1 Microfiltration of Coagulated Organic Solutions 15 5 5 .10 .2 hficrofiltration and Coagulation of Particle Suspensions 15 6 5 .11 SUMMARY 15 8 5 .12 CONCLUSION... Concentrates Method Selection A12 SURFACE WATER SOURCE A1.2 .1 Choice of Location A1.2.2 Kaw \X7ater Characteristics A1.3 MEMBRANE PROCESS OPERATION A1.3 .1 X1.3.2 X1.3.3 X1.3.4 316 316 317 318 Microfiltration and Reverse Osmosis Equipment Membrane Process Operation Freeze Drying Analysis A1.4 RESULTS A1.4 .1 X1.4.2 X1.4.3 A1.4.4 A1.4.5 X1.4.6 X1.4.7 A1.4.8 314 Flus and Water Permeability Organic Carbon Rejection... Chemical Pretreatment Effects in the Membrane Filtration of Waters containing Natural Organic Matter, 15 0 9 -1 517 , copyright 20 01, with permission from Elsevier Science: Tables 8 .1, 8 .11 , 8 .12 , 8 .14 , 8 .16 and Figures 8 .1, 8.2, 8.4, 8.5, 7.46, 8.7, 8 .1 1- 8 .13 Copyright © 20 01 by Andrea I Schafer Chapter 1 INTRODUCTION Copyright © 20 01 by Andrea I Schafer INTRODUCTION Surface water treatment is a controversial... Considerations 3 01 Copyright © 20 01 by Andrea I Schafer Contents 8.9 CONCLUSION XV 3 01 Chapter 9 - S.ummay ei.Concl.sion Chapter 10 - F.urtber Research Appendix 1 - Concentration ofNaturaI Organic Matter Al.l SELECTION OF CONCENTRATION METHOD XI 1. 1 A l 1. 2 X1 l 3 A l 1. 4 Conventional hlethods Concentration Using Membranes Comparison of Membrane and Adsorption Concentrates Method Selection A12 SURFACE... Copyright © 20 01 by Andrea I Schafer xvi Contents Appendix 3 - Hematite Pqbarution (C-F~~Q,) 4 1 A3 .1 SYNTHESIS OF HEMATITE PARTICLES 342 A3.2 CHARACTERISATION OF HEMATITE PARTICLES 343 Appendix 4 - Inshlnment Ca&ation A4 .1 ORGANIC CARBON ANALYSIS 34 7 348 A-+ l Introduction l X4 .1. 2 Principle A4 .1. 3 Oxidation Efficiency and Choice of Standards '14 1 .-+ Operation Mode ,\-l.Detection Limit 1. 5 '14 l 6 Errors...Contents xi 4 .10 .4 X-Ray Photoelectron Spectroscopy P P S ) 4 .10 .5 Contact Angle Measurements 4 .10 .6 Determination of Membrane Mass Deposit Chapter 5 - MicrojItration 13 1 5 .1 INTRODUCTION l32 5.2 FILTRATION PROTOCOL l33 5.3 MEMBRANE CHARACTERISATION l34 5.4 MF OF ORGANICS I N T H E ABSENCE O F INORGANIC COLLOIDS l36 5.5 MF O F INORGANIC COLLOIDS I N T H E ABSENCE O F ORGANICS 13 7 5.5 .1 Effect of Primary... OPS Systems Coagulation of SPO Systems Blochng Law Analysis 6.9 SUMMARY 211 6 .10 CONCLUSION 214 215 Chapter 7 - Nanojiltahon 7 .1 INTRODUCTION 216 7.2 FILTRATION PROTOCOL 216 7.2 .1 Membrane Compaction and Baseline 7.2.2 Protocol for Rejection Experiments 7.2.3 Protocol for Recycle Experiments 7.3 MEMBRANE CHARACTERISATION 219 7.3 .1 Effect of Temperature on Water Flux 7.3.2 7.3.3 7.3.4 7.3.5 Membrane 'Pore... 6 Errors and Interferences A4.2 UV/VIS ABSORBANCE 353 ,14 2 .1 hiethod -1 4.22 ,ibsorbance Characteristics of NOhf A4.2.3 Errors and Interferences Appendix 5 - Sohtion Speciation Using MinteqA2 A5 .1 INTRODUCTION - A5.2 MINTEOA2 SPECIATION CODE A 5 2 1 livailability of Sofhvare and Data Input A5.3 SPECIATION RESULTS ,-\ 5.3 .1 X5.3.2 A5.3.3 ii5.3.4 ,15 .3.5 358 358 358 359 pH Calculations as a Function of... greatly appreciated Desalination, 11 8, Schafer, A.I.; Fane, A.G.; Waite, T.D., Nanofiltration of Natural Organic Matter: Removal, Fouling and the Influence of Multivalent Ions, 10 9 -1 22, copyright 19 98, with permission from Elsevier Science: Tables 7 .10 , 7.25, 7.29, 7.30, 7.38, 7.47and Figures 4.4, 7.2, 7 .16 , 7. 21, 7.24, 7.38, 7.52 Journal of Colloid and Interface Science, 212 , Waite, T.D.; Schafer, A.I.;... with permission from Elsevier Science: Figures 4 .1 9- 4.23, 4. 31, 5 .1 - 5.5, 5. 7- 5 .11 Separation and Purification Technology, 2 2-2 3 Aoustin, E.; Schafer, A.I.; Fane, A.G.; Waite, T.D., Effect of Humic Substance and Colloid Interactions on Ultrafiltration Behaviour, 6 3-7 8, copyright 20 01, with permission from Elsevier Science: Table 5.8 and Figures 6.29 - 6.37 Water Science and Technology, (in press) . containing Natural Organic Matter, 15 0 9 -1 517 , copyright 20 01, with permission from Elsevier Science: Tables 8 .1, 8 .11 , 8 .12 , 8 .14 , 8 .16 and Figures 8 .1, 8.2, 8.4, 8.5, 7.46, 8.7, 8 .1 1-8 .13 . Copyright. NATURAL ORGANICS REMOVAL USING MEMBRANES Copyright © 20 01 by Andrea I. Schafer HOW TO ORDER THIS BOOK BY PHONE: 80 0-2 3 3-9 936 Or 71 7-2 91 -5 609, AM- PM Eastern Time BY FM: 71 7-2 9 5-4 538. Suspensions 15 6 5 .11 SUMMARY 15 8 5 .12 CONCLUSION 16 0 Copyright © 20 01 by Andrea I. Schafer xii Contents Chapter 6 - ULtrjZtration 16 1 6 .1 INTRODUCTION 16 3 6.2 FILTRATION PROTOCOL 16 3