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HYBRID PHOTOCATALYSIS AND MICROFILTRATION PRETREATMENT FOR ORGANIC FOULING CONTROL OF REVERSE OSMOSIS MEMBRANE LIU HONGYU NATIONAL UNIVERSITY OF SINGAPORE 2009 HYBRID PHOTOCATALYSIS AND MICROFILTRATION PRETREATMENT FOR ORGANIC FOULING CONTROL OF REVERSE OSMOSIS MEMBRANE LIU HONGYU (M. Eng., Beijing Univ. of Civil Eng. & Arch.) A THESIS SUBMITTED FOR THE DEGREE OF PHILOSOPHIAE DOCTOR DEPARTMENT OF CIVIL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2009 ACKNOWLEDGEMENT I wish to express my deepest appreciation and gratitude to my supervisor, Assoc. Prof. Ng How Yong, for his invaluable guidance, support, and encouragement throughout the entire research work. I would also like to extend my sincere gratitude to all technicians, staff and students, especially Mr. S.G. Chandrasegaran, Ms. Lee Leng Leng, Ms. Tan Xiaolan, Ms. Tan Hwee Bee, Ms. Ng Mei Joo and Mr. Tan Eng Hin, Michael, at the Environmental Engineering Laboratory of Division of Environmental Science and Engineering, National University of Singapore, for their assistance and cooperation in the many ways that made this research study possible. In addition, I wish to express my deep gratitude to National University of Singapore for financial support of my Ph.D study and various opportunities in academic activities. Special thanks also to be given to the Bedok and Ulu Pandan Water Reclamation Plant for the provision of raw water used in this study. Finally, I want to express my sincerest respect and thankfulness to my parents Mr LIU LianKao, Ms QI FuZhen, Elder sister LIU XiaoLuan and grandfather . I am deeply indebted to them for their everlasting support and encouragement in my study at Singapore. Without their endless encouragement and support, it would not be possible for me to complete my study. i TABLE OF CONTENTS Pages ACKNOWLEDGEMENT i TABLE OF CONTENTS .ii SUMMARY vi LIST OF TABLES .x LIST OF FIGURES xi LIST OF PLATES . xviii NOMENCLATURE .xix CHAPTER INTRODUCTION 1.1 Background 1.2 Objective and Scope 1.3 Organization of Thesis .5 CHAPTER LITERATURE REVIEW .8 2.1 Membrane Fouling .8 2.2 Membrane Fouling by EfOM .9 2.3 Membrane Fouling by NOM .15 2.4 Fouling Control Strategies .21 2.4.1 Conventional Pretreatment 21 2.4.2 Biofouling Prevention 23 2.4.3 MF/UF Membrane Pretreatment .25 2.5 Photocatalytic Reaction .27 2.6 Hybrid Membrane/Photocatalysis Process 33 2.7 Membrane Fouling Reduction by Photocatalytic Pretreatment .34 2.8 Summary 36 CHAPTER MATERIALS AND METHODS .39 ii 3.1 Photocatalysis Experiments .39 3.1.1 Catalysts .39 3.1.2 Feed Water .39 3.1.3 Photoreactor and UV Source .41 3.2 Crossflow RO Membrane Filtration Units .45 3.3 RO Membrane Fouling Experiments .47 3.4 Analytic Methods .48 3.4.1 Total Organic Carbon 48 3.4.2 Molecular Weight (MW) Distribution .48 3.4.3 UVA254, and Colour measurement (UVA430) 49 3.4.4 Contact Angle 50 3.4.5 Zeta Potential .50 3.4.6 Fourier Transform Infrared Spectroscopy (FTIR) .51 3.4.7 Excitation emission matrix (EEM) fluorescence spectroscopy and Synchronous fluorescence (SF) spectroscopy .52 CHAPTER NANO-SIZE TITANIA PHOTOCATALYSIS FOR ORGANIC FOULING ABATEMENT IN RO PROCESS IN THE RECLAMATION OF SECONDARY MUNICIPAL EFFLUENT .54 4.1 Introduction 54 4.2 Photocatalytic Oxidation of EfOM 57 4.3 EfOM Fouling on RO Membrane 65 4.3.1 Fouling Potential 65 4.3.2 Effect of Photocatalysis on Fouling Behaviors of EfOM 68 4.4 Changes in the Physicochemical Properties of EfOM .72 4.4.1 Molecular Weight Distribution 72 4.4.2 Hydrophobicity (SUVA and Contact angles) and Color of EfOM iii 74 4.4.3 Fluorescence Spectrum of EfOM 80 4.4.4 FTIR Spectrum 83 4.5 Conclusion .85 CHAPTER PHOTOCATALYTIC PRETREATMENT OF LOW CONCENTRATION SODIUM ALGINATE AND IMPACT ON ITS FOULING BEHAVIORS 88 5.1 Introduction 88 5.2 Photocatalytic Oxidation of Polysaccharide 90 5.3 Polysaccharide Fouling on RO Membrane 95 5.3.1 Fouling Potential 95 5.3.2 Influence of Electrolytes on Fouling .99 5.3.2.1 No External Electrolytes 100 5.3.2.2 Ionic Strength .102 5.3.2.3 The Effect of Calcium 103 5.3.3 Influence of Feed Foulant Composition on Fouling 106 5.3.4 Influence of Initial Concentration of Polysaccharides on Fouling 109 5.3.5 Influence of UV Sources on Fouling .112 5.3.6 Influence of Reaction Time on Fouling .113 5.3.7 Influence of Catalyst Concentrations on Fouling 116 5.4 Changes in the Physicochemical Properties of Polysaccharides .118 5.4.1 Molecular Weight Distribution 118 5.4.2 Zeta Potential .120 5.4.3 FTIR Spectrum 123 5.5 Conclusion .124 iv CHAPTER IMPACT OF PHOTOCATALYTIC PRETREATMENT ON REVERSE OSMOSIS MEMBRANE FOULING BY LOW CONCENTRATION NATURAL ORGANIC MATTERS .126 6.1 Introduction 126 6.2 Photocatalytic Oxidation of SRNOM 128 6.3 SRNOM Fouling on RO Membrane 133 6.3.1 Influence of Electrolytes on Fouling .133 6.3.1.1 No External Electrolytes 134 6.3.1.2 Ionic Strength .136 6.3.1.3 The Effect of Calcium 137 6.3.2 Influence of Feed Foulant Composition on Fouling 142 6.3.3 Influence of UV Sources on Fouling .143 6.4 Changes in the Physicochemical Properties of SRNOM .145 6.4.1 Hydrophobicity (SUVA values) and Color of SRNOM 145 6.4.2 Fluorescence Spectrum of SRNOM 149 6.4.3 Molecular Weight Distribution 155 6.4.4 Zeta Potential .157 6.4.5 FTIR Spectrum 160 6.5 Conclusion .162 CHAPTER CONCLUSIONS AND RECOMMENDATIONS 164 7.1 Conclusions 164 7.2 Recommendations for further research 166 REFERENCES 170 v SUMMARY Organic fouling caused by aqueous organic matters (AOM) from secondary effluents or natural water bodies has been the prime bottleneck hindering the widespread applications of RO membrane technology. These organic matters tend to absorb or deposit on RO membrane surface and often cause reversible or irreversible fouling. The costs associated with organic fouling abatement and the resultant flux decrease usually contribute to a significant fraction of the total cost of the membrane processes. The conventional pretreatment methods, such as coagulation/flocculation, have never satisfactorily prevented the fouling associated with aqueous biopolymers, such as the polysaccharides, protein, and natural organic matter (NOM). Moreover, due to the abundance and complexity of AOM in aquatic environment, conventional pretreatment measures cannot readily achieve stable performances. Even emerging membrane pretreatment system using low pressure driven membranes, such as microfiltration (MF), ultrafiltration pretreatment, or nanofiltration, which itself is susceptible to organic fouling by AOM, cannot address the problem over a long-term operation. Hence, it is timely and important to develop an alternative method for effective alleviation and control of organic fouling in RO process. The primary objective of this study was to develop a novel pretreatment method - hybrid photocatalysis and microfiltration process - for RO membrane fouling control in the water reclamation process. In this study, TiO2-based photocatalytic reaction combined with MF process was employed as pretreatment process for fouling reduction of RO membrane, vi with effluent organic matters (EfOM), a model hydrophilic polysaccharide (sodium alginate), a model protein (Bovine serum albumin) and Suwannee River NOM of hydrophobic propensity as foulants operated in a lab-scale cross flow RO membrane filtration system. Factors influencing the fouling potential of the feed solution were investigated. The hybrid system provided a good alternative to effectively control the organic fouling development on RO membrane. In the presence of UV light and nano-size TiO2, photocatalytic reaction within relatively short reaction time favorably changed the physicochemical properties of the reactants, such as the molecular weight distribution, functional groups, charge densities, etc, which were revealed by the tests of chromatography, high pressure Fluorescence liquid chromatography-size excitation–emission-matrix exclusion spectrum, Synchronous fluorescence spectrum, Fourier transform infrared spectroscopy, UV spectrum and Zeta potential, etc. At relatively low TOC concentration, the fouling potential, k, on RO membrane, a parameter for qualitative measurement of fouling tendency, was significantly lowered in the fouling tests with EfOM, polysacchrides and SRNOM, especially in the presence of calcium by photocatalytic pretreatment. This reduction could be ascribed to the changes in the properties of AOM introduced by photocatalysis, leading to attenuated intermolecular actions among organic molecules and reduced interactions between the organic molecules and RO membrane surface. The macromolecules of the hydrophobic matters could be degraded into less hydrophobic micromolecules, resulting in the decrease in their fouling potentials. These reductions were also significant for hydrophilic polysaccharides in the presence of Ca2+ due to the weakened intermolecular vii bridging effect on micromolecules, leading to a less dense fouling layer on membrane surface. These findings are of crucial importance in starting a new scenario in the study of organic fouling alleviation. 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Chemosphere 2002;48(1):59-68. 184 185 [...]... minor modification of the functional groups of the substrate and decreasing membrane fouling by biopolymers associated with microorganism Therefore it is a possible process for organic fouling control in membrane process Our aim in this research was to develop a novel pretreatment measure for organic fouling control of RO process by a hybrid photocatalysis process and low-pressure-driven membrane process,... also associated with membrane fouling The current understanding of all of these chemical and physical interactions is still insufficient to provide a comprehensive and systematic understanding of membrane fouling Organic fouling by aqueous organic matters and biofouling caused by an active biofilm remain as the major problems in membrane- related water and wastewater processes Organic foulants in aqueous... because of its high effectiveness in removing particles, including microorganisms, organic pollutants, inorganic salts, and achieving a biologically stable water However, membrane fouling is still a major obstacle for wide-scale application of this technology Several types of fouling can occur in membrane systems including inorganic fouling, particulate and colloidal fouling, organic fouling, and biofouling... LITERATURE REVIEW 2.1 Membrane Fouling Membrane systems - Microfiltration/ Ultrafiltration (MF/UF) and Nanofiltration/ Reverse Osmosis (NF/RO) - are increasingly being applied for water and wastewater treatment and water reclamation The choice of membrane, module configuration, process and operating parameters, and pretreatment are very important factors affecting efficiency of separation Membrane technology... effects of membrane fouling [1-3] 1 Chapter 1 The costs associated with fouling control and abatement usually contribute to a significant fraction of the total cost of the membrane processes Membrane fouling is inevitable in membrane filtration processes [1-3] and the reduction of fouling propensity of the feed water with the appropriate treatment is one of the most serious considerations of membrane. .. hydrophilic polysaccharides and effluent organic matters, and to investigate the possible mechanisms of changes in fouling potentials and the correlation between physicochemical property changes and fouling behaviors (iv) RO membrane fouling alleviation with hybrid pretreatment - to compare and optimize the fouling control efficiency for various membrane /photocatalysis configuration factors, and to investigate... process Fouling control mechanisms was elucidated for major organic matters in the biologicallytreated sewage effluent, such as polysaccharides, protein, and natural organic matter (NOM), and the fouling control efficiency was optimized 1.2 Objective and Scope The overall objective of this proposed study was to develop a hybrid photocatalysis/ membrane pretreatment system for effective alleviation and control. .. Accordingly, SMP fouling is one of the major types of fouling in the RO process and it was found to provide high membrane fouling potential during water reclamation/reuse [26] Microorganisms and their SMP have been found to be the major source of membrane biofouling in the wastewater reclamation system especially in the RO, NF processes Biofouling is more complicated than other membrane fouling phenomena Fouling. .. processes Organic fouling and biofouling are regarded as the two major types of fouling for membrane related to water and wastewater treatment that can be less effectively abated by common pretreatment measures The common pretreatment measures, such as coagulation/flocculation, sedimentation, and filtration, are more effective for particulate and colloidal foulants At very low concentrations, aqueous organic. .. blocking and cake formation are considered as the two main mechanisms of membrane fouling while other factors such as adsorption, particle deposition within the pores, etc also have some effect on the fouling formation [13] Membrane fouling is an extremely complex physicochemical phenomenon Fouling of membrane is determined by the composition of the feed water and the physical-chemical properties of membranes . HYBRID PHOTOCATALYSIS AND MICROFILTRATION PRETREATMENT FOR ORGANIC FOULING CONTROL OF REVERSE OSMOSIS MEMBRANE LIU HONGYU NATIONAL UNIVERSITY OF SINGAPORE. 2009 HYBRID PHOTOCATALYSIS AND MICROFILTRATION PRETREATMENT FOR ORGANIC FOULING CONTROL OF REVERSE OSMOSIS MEMBRANE LIU HONGYU (M. Eng., Beijing Univ. of Civil Eng method for effective alleviation and control of organic fouling in RO process. The primary objective of this study was to develop a novel pretreatment method - hybrid photocatalysis and microfiltration