A STUDY ON ORGANIC FOULING OF REVERSE OSMOSIS MEMBRANE MO HUAJUAN (B.&M.Eng., ECUST) A THESIS SUBMITTED FOR THE DEGREE OF PhD OF ENGINEERING DEPARTMENT OF CIVIL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2009 Acknowledgement Acknowledgement This is for me an enriching journey of challenges, opportunities, and excitement. Without the many wonderful people to whom I owe millions of supports and help, it could be impossible. My deepest appreciation goes to my supervisor Associate Professor Ng How Yong and Professor Ong Say Leong for their constant encouragement, invaluable guidance, patience and understanding in research and life throughout the whole length of my PhD candidature. Special thanks also to all the laboratory officers, friends and my family; as well as anyone who have helped me in one way or another during my PhD study. i Table of contents Table of Contents Acknowledgement i  Table of Contents ii  vii   Summary List of Tables ix  List of Figures x  Nomenclature xv  Chapter Introduction 1  1.1 Background 2  1.2 Problem statement 7  1.3 Research objectives 10  1.4 Organization of thesis 12  Chapter Literature Review 2.1 Dissolved organic matters in water reclamation system 15  15  2.1.1 Source of dissolved organic matters 15  2.1.2 Dissolved organic matters removal by MF/UF 17  2.1.3 Model polysaccharides and proteins 18  2.2 Membrane and membrane process system 21  2.2.1 Membrane definition and process classification 21  2.2.2 Basic membrane transport theory for RO process 24  2.2.3 Concentration polarization 26  ii Table of contents 2.2.4 Spiral wound membrane module and the permeate flux behavior 2.3 Membrane fouling 29  33  2.3.1 Definition and types of membrane fouling in RO process 33  2.3.2 Fouling mechanisms in RO process 35  2.3.3 Key issues in organic fouling 37  2.3.4 Membrane cleaning 46  Chapter Materials and Methods 50  3.1 Chemical solution preparation 50  3.1.1 Model organic matters 50  3.1.2 Other chemicals 50  3.2 RO membranes 51  3.3 RO filtration setup 52  3.3.1 Small lab-scale crossflow membrane cell 52  3.3.2 Long channel crossflow RO membrane cell 54  3.4 Filtration and cleaning operation 57  3.4.1 Salt solution filtration tests 57  3.4.2 Organic fouling tests 57  3.4.3 Cleaning tests 58  3.5 Membrane hydraulic resistance measurement 59  3.6 Beaker tests of gel formation 60  3.7 Analytical techniques 60  3.7.1 Streaming potential analyzer 60  3.7.2 SEM-EDX 61  3.7.3 Polysaccharide and protein assay 62  iii Table of contents Chapter Polysaccharide Fouling and Chemical Cleaning 4.1 Polysaccharide fouling 63  64  4.1.1 Effects of calcium concentration on alginate fouling 64  4.1.2 Effects of alginate concentration on alginate fouling 65  4.1.3 Gel formation in beaker tests 68  4.2 Chemical cleaning of membranes fouled by polysaccharide 70  4.2.1 Effects of calcium on membrane cleaning 70  4.2.2 Effects of pH and concentration of cleaning solution 72  4.2.3 Impact of multiple cleaning cycles 76  4.3 Summary Chapter Protein Fouling and Chemical Cleaning 5.1 Protein fouling 78  79  79  5.1.1 Adsorption of BSA on membrane 79  5.1.2 Effects of ionic strength 81  5.1.3 Effects of cations 84  5.1.4 Effects of temperature 89  5.2 Chemical cleaning of membranes fouled by protein 93  5.2.1 Effects of cleaning solution concentration 93  5.2.2 Effects of cleaning solution pH 95  5.2.3 Effects of cleaning time 96  5.3 Summary 98  iv Table of contents Chapter Permeate Behavior and Concentration Polarization in a Long RO Membrane Channel 100  6.1 Calculation of concentration polarization 101  6.2 Variation of permeate flux along the channel 104  6.3 Variation of rejection along the channel 109  6.4 CP and CF variation along the channel 112  6.5 Correlation between recovery and CP 115  6.6 Permeate performance in a spacer-filled channel 119  6.6 Summary 124  Chapter Organic Fouling Development in a Long RO Membrane Channel 127  7.1 Organic fouling development along the channel 128  7.1.1 The permeate behavior in alginate and BSA fouling along the RO membrane channel 128  7.1.2 Effects of operating conditions on organic fouling development along the channel 7.1.3 Effects of feed spacer(s) on alginate fouling 133  138  7.2 Key factors in organic fouling development in a long membrane channel and numerical study 139  7.2.1 Model development 140  7.2.2 Comparison between experimental work and numerical simulation 7.3 Summary 145  149  v Table of contents Chapter Conclusions and Recommendations 151  8.1 Conclusions 152  8.2 Recommendations 155  References 158  Appendix 170  vi Summary Summary Reverse osmosis (RO) is a valuable membrane separation process and is increasingly used in water reclamation because of its high product quality and low costs. The efficiency of RO membrane is limited most notably by membrane fouling, which refers to the accumulation of foulant present even in minute quantity in the RO feed. An understanding of the feed solution, that is, the foulant composition, is the first step towards formulating a fouling mitigation strategy. Within the commonly encountered foulants in water reclamation, organic fouling is a major category which include humic acids, polysaccharides, proteins, etc. A key issue in organic fouling is the various interactions between organic foulants, inorganic components of the feed and the RO membranes. Typically, a small lab-scale RO membrane cell can be used to investigate the organic fouling behavior, but it cannot completely represent what actually happens in a membrane module. The full-scale RO membrane channel has been theoretically shown to be of a heterogeneous system, which is characterized by variation of water flow and mass concentration along the flow channel. These variable parameters will inevitably affect the distribution of the deposited organic foulants. Hence, compared with an average permeate flux, local permeate flux is more reliable to describe the fouling development in RO membrane channel, which will add further to our knowledge on organic fouling in a real plant. vii Summary In this thesis, sodium alginate and bovine serum albumin (BSA) chosen as model polysaccharide and protein, respectively, were used to study the polysaccharide and protein fouling behavior in two lab-scale RO membrane cells of different dimensions. The first test cell was 0.1 m long and was treated as a homogenous system while the second one was a 1-m long cell which was designed to measure five local permeate flux along the channel. The study began with an investigation of RO membrane fouling by alginate. The presence of calcium in the feed solution intensively magnified alginate fouling potential. Other chemical (pH, ionic strength, cation species) and physical (temperature) parameters of feed water were investigated in the study of RO membrane fouling by BSA. It is noted that the most severe BSA fouling occurred at pH near the iso-electric point (IEP) of BSA. The study proceeded with an investigation into the behavior of permeate flux in a long RO membrane channel. This is the first report to experimentally show the heterogeneous distribution of flow and mass due to exponential growth of salt concentration polarization in a long RO membrane channel. Interestingly, in this long membrane channel, permeate flux was observed to decline faster at one end than the other end of the channel when the organic fouling progressed. In addition, modeling efforts simulated the alginate fouling development in the 1-m long RO membrane channel by incorporating a modified fouling potential and deposition ratio and predicted well the experimental results. viii List of tables List of Tables Table 2.1 Some membrane processes and their driving forces (Mulder, 1996). Table 2.2 Classification of pressure-driven membrane processes (Mulder, 1996). Table 2.3 Empirical relations of the concentration dependence of osmotic pressure for different salt (Lyster and Cohen, 2007). Table 3.1 Surface characterization of LFC1 and ESPA2 RO membrane. Table 4.1 Atomic weight percentage on the membrane surface by SEM-EDX. Table 7.1 RO parameter values for simulation. ix Conclusions and recommendations be improved to characterize organic fouling apart from colloid fouling. If the fouling potential characterization for all the fouling types can be expressed in a value or a simple mathematical equation, the fouling in RO process can be estimated more accurately. The costs and efforts invested to distinguish the different foulants in the feed can be greatly saved. 3. Implementation of pilot-scale study Much effort in this study is based on experimental test using lab-scale RO membrane setup. Even the long channel membrane cell is only one meter in length and is much shorter than the actual RO process, which typically consists of modules in one pressure vessel. Pilot scale studies have to be implemented to observe concentration polarization growth and organic or other fouling development along the actual RO membrane channel. Pilot scale studies can verify the fouling characteristics obtained from this lab-scale study and the effectiveness of the organic fouling factors proposed in the predictive model in this study. At present, the pilot study used a global average flux to characterize the fouling and no additional samples except the final permeate can be taken and measured. Therefore, a modified pilot setup is needed to measure the permeate flux and concentration at the end of each RO membrane module. 157 References References Abu Tarboush, B.J., D. Rana, T. Matsuura, H.A. Arafat, and R.M. Narbaitz. Preparation of thin-film-composite polyamide membranes for desalination using novel hydrophilic surface modifying macromolecules. J. Membr. Sci., 325, 166-175, 2008. Ahmad, A.L., K.K. Lau, and M.Z. Abu Bakar. Impact of different spacer filament geometries on concentration polarization control in narrow membrane channel. J. Membr. Sci., 262, 138-152, 2005. Al-Bastaki, N.M., and Abbas, A. Predicting the performance of RO membranes. Desalination, 132, 181-187, 2000. Ang, W.S., S. Lee, and M. Elimelech. Chemical and physical aspects of cleaning of organic-fouled reverse osmosis membranes. J. Membr. Sci., 272, 198-210, 2006. Ang, W.S., and Elimelech, M. Protein (BSA) fouling of reverse osmosis membranes: Implications for wastewater reclamation. J. Membr. Sci., 296, 83-92, 2007. Aptel, P., and Buckley, C.A. Categories of membrane operations in Water Treatment Membrane Process ed. By Mallevialle et al. New York: McGraw Hill. 1996. Avlonitis, S., W.T. Hanbury, and M.B. Boudinar. Spiral wound modules performance an analytical solution: part II. Desalination, 89, 227-246, 1993. Barker, D.J., and Stuckey, D.C. A review of soluble microbial products (SMP) in wastewater treatment systems. Wat. Res., 33, 3063-3082, 1999. Bellona, C., J.E. Drewes, P. Xu, and G. Amy. Factors affecting the rejection of organic solutes during NF/RO treatment — a literature review. Wat. Res., 38, 27952809, 2004. Bessiere, Y., D.F. Fletcher, and P. Bacchin. Numerical simulation of colloid dead-end filtration: Effect of membrane characteristics and operating conditions on matter accumulation. J. Membr. Sci., 313, 52-59, 2008. Bhattacharyya, D., S.L. Back, R.I. Kermode, and M.C. Roco. Prediction of concentration polarization and flux behavior in reverse osmosis by numerical analysis. J. Membr. Sci., 48, 231-262, 1990. Bloomfield, V. The structure of bovine serum albumin at low pH. Biochemistry, 5, 684-689, 1966. 158 References Bos, M.A., Z. Shervani, A.C.I. Anusiem, M. Giesbers, W. Norde, and J.M. Kleijn, Influence of the electric potential of the interface on the adsorption of proteins. Colloids Surf. B: Biointerf., 3, 91-100, 1994. Bouchard, C.R., P.J. Carreau, T. Matsuura, and S. Sourirajan. Modeling of ultrafiltration: predictions of concentration polarization effects. J. Membr. Sci., 97, 215-229, 1994. Brauns, E., E.V. Hoof, B. Molenberghs, C. Dotremont, W. Doyen, and R. Leysen. A new method of measuring and presenting the membrane fouling potential. Desalination, 150, 31-43, 2002. Brandt, D.C., G.F. Leitner, and W.E. Leitner. Reverse osmosis membranes state of the art in Reverse osmosis membrane technology, water chemistry, and industrial applications ed. by Z. Amjad. New York: Van Nostrand Reinhold. 1993. Bruus, J.H., P.H. Nielsen, and K. Keiding. On the stability of activated sludge flocs with implications to dewatering. Wat. Res., 26, 1597-1604, 1992. Bu-Ali, Q., M. Al-Aseeri, and N. Al-Bastaki. An experimental study of performance parameters and ion concentration along a reverse osmosis membrane. Chem. Eng. Process., 46, 323-328, 2007. Bu, H., A.-L. Kjøniksen, A. Elgsaeter, and B. Nyström. Interaction of unmodified and hydrophobically modified alginate with sodium dodecyl sulfate in dilute aqueous solution: Calorimetric, rheological, and turbidity studies. Colloid Surf. A: Physicochem. Eng. Asp., 278, 166-174, 2006. Bu, H., A.-L. Kjøniksen, K.D. Knudsen, and B. Nyström. Effects of surfactant and temperature on rheological and structural properties of semidilute aqueous solutions of unmodified and hydrophobically modified alginate. Langmuir, 21, 10923-10930, 2005. Byrne, W. Reverse Osmosis- A practical guide for industrial users. Littleton: Tall Oaks Publishing, Inc. 1995. Campbell, M.J., R.P. Walter, R. McLoughlin, and C.J. Knowles. Effect of temperature on protein conformation and activity during ultratfiltration. J. Membr. Sci., 78, 3543, 1993. Chen, K.L., L. Song, S.L. Ong, and W.J. Ng. The development of membrane fouling in full-scale RO processes. J. Membr. Sci., 232, 63-74, 2004. Chen, V., R. Chan, H. Li, and M.P. Buchnall. Spatial distribution of foulants on membranes during ultrafiltration of protein mixtures and the influence of spacers in the channel. J. Membr. Sci., 287, 79-87, 2007. Chilukuri, V.V.S., A.D. Marshall, P.A. Munro, and H. Singh. Effect of sodium dodecyl sulphate and cross-flow velocity on membrane fouling during cross-flow microfiltration of lactoferrin solutions. Chem. Eng. Process., 40, 321-328, 2001. 159 References Clifton, M.J., N. Abidine, P. Aptel, and V. Sanchez. Growth of the polarization layer in ultrafiltration with hollow-fiber membranes. J. Membr. Sci., 21, 233-246, 1984. Cohen, R.D., and Probstein, R.F. Colloidal fouling of reverse osmosis membranes. J. Colloid Interface Sci., 114, 194-207, 1986. Combe, C., E. Molis, P. Lucas, R. Riley, and M.M. Clark. The effect of CA membrane properties on adsorptive fouling by humic acid. J. Membr. Sci., 154, 73-87, 1999. Compbell, M.K., and Farrell, S.O. Biochemistry. Brooks/Cole, California, 2006. Dacosta, A.R. Fluid flow and mass transfer in spacer-filled channels for ultrafiltration. Ph.D. Thesis, School of Chemical Engineering and Industrial Chemistry, University of New South Wales, 1993. Davis, R.H. Modeling of fouling of crossflow microfiltration membranes. Sep. Purif. Meth., 21, 75-126, 1992. Davis, T.A., F. Llanes, B. Volesky, and A. Mucci. Metal selectivity of Sargassum spp. and their alginates in relation to their α-L–guluronic acid content and conformation. Environ. Sci. Technol., 37, 261-267, 2003. de Pinho, M.N., V. Semião, and V. Geraldes. Integrated modeling of transport processes in fluid/nanofiltration membrane systems. J. Membr. Sci., 206, 189-200, 2002. Dignac, M.-F., V. Urbain, D. Rybacki, A. Bruchet, D. Snidaro, and P. Scribe. Chemical description of extracellular polymers: implication on activated sludge floc structure. Wat. Sci. Tech., 38, 45-53, 1998. DuBois, M., K.A. Gilles, J.K. Hamilton, P.A. Rebers, and F. Smith. Colorimetric method for determination of sugars and related substances. Anal. Chem., 28, 350-356, 1956. El Kadi, N., N. Taulier, J.Y. Le Huérou, M. Gindre, W. Urbach, I. Nwigwe, P.C. Kahn, and M. Waks. Unfolding and refolding of bovine serum albumin at acid pH: ultrasound and structural studies. Biophys. J., 91, 3397-3404, 2006. Elimelech, M., X. Zhu, A.E. Childress, and S. Hong. Role of membrane surface morphology in colloidal fouling of cellulose acetate and composite aromatic polyamide reverse osmosis membranes. J. Membr. Sci., 127, 101-109, 1997. Elimelech, M., W.H. Chen, and J.J. Waypa. Measuring the zeta (electrokinetic) potential of reverse osmosis membrane by a streaming potential analyzer. Desalination, 95, 269286, 1994. Elzo, D., P. Schmita, D. Houi, and S. Joscelyne. Measurement of particle/membrane interactions by a hydrodynamics method. J. Membr. Sci., 109, 43-53, 1996. 160 References Fairbrother, F., and Mastin, H. Studies in electro-endosmosis. J. Chem. Soc., 125, 2319-2330, 1924. Fariñas, M., J.M. Granda, L. Gurtubai, and M.J. Villagra. Pilot experiences on the recovery of polluted reverse osmosis membranes. Desalination, 66, 385-402, 1987. Frank, B.P., and Belfort, G. Polysaccharides and sticky membrane surfaces: critical ionic effects. J. Membr. Sci., 212, 205-212, 2003. Fu, X., T. Maruyama, T. Sotani, and H. Matsuyama. Effect of surface morphology on membrane fouling by humic acid with the use of cellulose acetate butyrate hollow fiber membranes. J. Membr. Sci., 320, 483-491, 2008. Geraldes, V., V. Semião, and M.N. de Pinho. Flow and mass transfer modeling of nanofiltration. J. Membr. Sci., 191, 109-128, 2001. Gerard, R., H. Hachisuka, and M. Hirose. New membrane developments expanding the horizon for the application of reverse osmosis technology. Desalination, 119, 4755, 1998. Goosen, M.F.A., S.S. Sablani, H. Ai-Hinai, S. Ai-Obeidani, R. Al-Belushi, and D. Jackson. Fouling of reverse osmosis and ultrafiltration membranes: a critical review. Sep. Sci. Technol., 39, 2261- 2297, 2004. Grant, G.T., E.R. Morris, R.A. Rees, P.J.C. Smith, and D. Thom. Biological interactions between polysaccharides and divalent cations: the egg-box model. FEBS LETTERS, 32, 195-198, 1973. Grover, P.K., and Ryall, R.L. Critical appraisal of salting-out and its implications for chemical and biological sciences. Chem. Rev., 105, 1-10, 2005. Gupta, S.K. Design and analysis of reverse osmosis system using three parameter models for transport across the membrane. Desalination, 85, 283- 296, 1992. Güell, C., and Davis, R.H. Membrane fouling during microfiltration of protein mixtures. J. Membr. Sci., 119, 269284, 1996. Haarhoff, J., and van der Merwe, B. Twenty-five years of wastewater reclamation in Windhoek, Namibia. Wat. Sci. Tech., 33, 25-35, 1996. Herzberg, M., and Elimelech, M. Biofouling of reverse osmosis membranes: role of biofilm-enhanced osmotic pressure. J. Membr. Sci., 295, 11-20, 2007. Herzberg, M., S. Kang, and M. Elimelech. Role of extracellular polymeric substances (EPS) in biofouling of reverse osmosis membranes. Environ. Sci. Technol., 43, 43934398, 2009. Hoek, E.M.V., and Elimelech, M. Cake-enhanced concentration polarization: a new fouling mechanism for salt-rejecting membranes. Environ. Sci. Technol., 37, 55815588, 2003. 161 References Hoek, E.M.V., J. Allred, T. Knoell, and B.-H. Jeong. Modeling the effects of fouling on full-scale reverse osmosis processes. J. Membr. Sci., 314, 33-49, 2008. Hong, S., and Elimelech, M. Chemical and physical aspects of natural organic matter (NOM) fouling of nanofiltration membranes. J. Membr. Sci., 132, 159-181, 1997. Hong, S., R.S. Faibish, and M. Elimelech. Kinetics of permeate flux decline in crossflow membrane filtration of colloidal suspensions. J. Colloid Interface Sci., 196, 267-277, 1997. Hu, J.Y., S.L. Ong, J.H. Shan, J.S. Kang, and W.J., Ng. Treatability of organic fractions derived from secondary effluent by reverse osmosis membrane. Wat. Res., 37, 4801-4809, 2003. Imai, A., T. Fukushima, K. Matsushige, Y.-H. Kim, and K. Choi. Characterization of dissolved organic matter in effluents from wastewater treatment plants. Wat. Res., 36, 859-870, 2002. Jacangelo, J.G, J.-M. Laine, E.W. Cummins, and S.S. Adham. UF with pretreatment for removing DSP precursors. J. AWWA, 3, 100-112, 1987. Jaffrin, M.Y. Dynamic shear-enhanced membrane filtration: a review of rotating disks, rotating membranes and vibrating systems. J. Membr. Sci., 324, 7-25, 2008. Jarusutthirak, C., G. Amy, and J.-P. Croué. Fouling characteristics of wastewater effluent organic matter (EfOM) isolates on NF and UF membranes. Desalination, 145, 247-255, 2002. Jones, K.L., and O’Melia, C.R. Protein and humic acid adsorption onto hydrophilic membrane surfaces: effects of pH and ionic strength. J. Membr. Sci., 165, 31-46, 2000. Kelly, S.T., and Zydney, A.L. Effects of intermolecular thiol-disulfide interchange reactions on BSA fouling during microfiltration. Biotechnol. Bioeng., 44, 972-982, 1994. Kimura, K., Y. Hane, Y. Watanabe, G. Amy, and N. Ohkuma. Irreversible membrane fouling during ultrsfiltrstion of surface water. Wat. Res., 38, 3431-3441, 2004. Koutsou, C.P., S.G. Yiantsios, and A.J. Karabelas. A numerical and experimental study of mass transfer in spacer-filled channels: Effects of spacer geometrical characteristics and Schmidt number. J. Membr. Sci., 326, 234-251, 2009. Kuzmenko, D., E. Arkhangelsky, S. Belfer, V. Freger, and V. Gitis. Chemical cleaning of UF membranes fouled by BSA. Desalination, 179, 323-333, 2005. Lapointe, J.-F., S.F. Gauthier, Y. Pouliot, and C. Bouchard. Fouling of a nanofiltration membrane by β-lactoglobulin tryptic hydrolysate: impact on the membrane sieving and electrostatic properties. J. Membr. Sci., 253, 89-102, 2005. 162 References Lattner, D., H.-C. Flemming, and C. Mayer. 13C-NMR study of the interaction of bacterial alginate with bivalent cations. Int. J. Biol. Macromol., 33, 81-88, 2003. Lawrence, N.D., J.M. Perera, M. Iyer, M.W. Hickey, and G.W. Stevens. The use of streaming potential measurements to study the fouling and cleaning of ultrafiltration membranes. Sep. Purif. Technol., 48, 106-112, 2006. Le Gouellec, Y.A., and Elimelech, M. Calcium sulfate (gypsum) scaling in nanofiltration of agriculture drainage water. J. Membr. Sci., 205, 279-291, 2002. Lee, H., G. Amy, J. Cho, Y. Yoon, S.-H. Moon, and I.S. Kim. Cleaning strategies for flux recovery of an ultrafiltration membrane fouled by natural organic matter. Wat. Res., 35, 3301-3308, 2001. Lee, S., J. Cho, and M. Elimelech. Combined influence of natural organic matter (NOM) and colloidal particles on nanofiltration membrane fouling. J. Membr. Sci., 262, 27-41, 2005. Lee, S., W.S. Ang, and M. Elimelech. Fouling of reverse osmosis membranes by hydrophilic organic matter: implications for water reuse. Desalination, 187, 313-321, 2006. Li, Q., and Elimelech, M. Organic fouling and chemical cleaning of nanofiltration membrane: measurements and mechanisms. Environ. Sci. Technol., 38, 4683-4693, 2004. Li, Q., Z. Xu, and I. Pinnau. Fouling of reverse osmosis membranes by biopolymers in wastewater secondary effluent: Role of membrane surface properties and initial permeate flux. J. Membr. Sci., 290, 173-181, 2007. Li, X., J. Li, X. Fu, R. Wickramasinghe, and J. Chen. Chemical cleaning of PS ultrafilters fouled by the fermentation broth of glutamic acid. Sep. Purif. Technol., 42, 181-187, 2005. Lin, C.-F., S.-H. Liu, and O.J. Hao. Effect of functional groups of humic substances on UF performance. Wat. Res., 35, 2395-2402, 2001. Lin, S.-H., C.-L. Hung, and R.-S. Juang. Effect of operating parameters on the separation of protein in aqueous solutions by dead-end ultrafiltration. Desalination, 234, 116-125, 2008. Lowry, O.H., N.J. Rosebrough, A.L. Farr, and R.J. Randall. Protein measurement with the folin phenol reagent. J. Biol. Chem., 193, 265-275, 1951. Lyster, E., and Cohen, Y. Numerical study of concentration polarization in a rectangular reverse osmosis membrane channel: Permeate flux variation and hydrodynamics end effects. J. Membr. Sci., 303, 140-153, 2007. 163 References Ma, H., H.E. Allen, and Y. Yin. Characterization of isolated fractions of dissolved organic matter from natural waters and a wastewater effluent. Wat. Res., 35, 985-996, 2001. Madaeni, S.S., and Mansourpanah, Y. Chemical cleaning of reverse osmosis membranes fouled by whey. Desalination. 161, 13-24, 2004. Madaeni, S.S., T. Mohamamdi, and M.K. Moghadam. Chemical cleaning of reverse osmosis membrane. Desalination. 134, 77-82, 2001. Maruyama, T., S. Katoh, M. Nakajima, H. Nabetani, T.P. Abbott, A. Shono and K. Satoh. FT-IR analysis of BSA fouled on ultrafiltration and microfiltration membranes. J. Membr. Sci., 192, 201-207, 2001. Matthiasson, E. The role of macromolecular adsorption in fouling of ultrafiltration membranes. J. Membr. Sci., 16, 23-36, 1983. Meireles, M., P. Aimar, and V. Sanchez. Albumin denaturation during ultrafiltration: Effects of operating conditions and consequences on membrane fouling. Biotechnol. Bioeng., 38, 528534, 1991. Metcalf & Eddy, Inc. Wastewater engineering treatment and reuse. 4th ed. McGrawHill, New York, 2004. Michaels, A.S. New separation technique for the CPI. Chem. Eng. Prog., 64, 3143,1968. Michnik, A., K. Michalik, and Z. Drzazga. Stability of bovine serum albumin at different pH. J. Therm. Anal. Cal., 80, 399-406, 2005. Mueller, J., and Davis, R.H. Protein fouling of surface-modified polymeric microfiltration membranes. J. Membr. Sci., 116, 4760, 1996. Mujeirigo, R. Achievements and challenges in the reuse of reclaimed water. Presentations and articles Euro-CAE workshop “wastewater as resource”. Paris, Institute de France, July 2000. Mulder, M. Basic Principles of Membrane technology. 2rd ed. London: Kluwer Academic Publishers. 1996. Muñoz-Aguado, M.J., D.E. Wiley, and A.G. Fane. Enzymatic and detergent cleaning of a polysulfone ultrafiltration membrane fouled with BSA and whey. J. Membr. Sci., 117, 175-187, 1996. Murrer, J., and Latter, S. Reducing the costs of ultrapure water production. Alpheus International Ltd. Available via www.Alpheus.co.uk, І-3. 2003. Murthy, Z.V.P., and Gupta, S.K. Estimation of mass transfer coefficient using a combined nonlinear membrane transport and film theory model. Desalination, 109, 39-49, 1997. 164 References Nakamura, K., and Matsumoto, K. Properties of protein adsorption onto pore surface during microfiltration: Effects of solution environment and membrane hydrophobicity. J. Membr. Sci., 280, 363374, 2006. Neal, P.R., H. Li, A.G. Fane, and D.E. Wiley. The effect of filament orientation on critical flux and particle deposition in spacer-filled channels. J. Membr. Sci., 214, 165-178, 2003. Nemeth, J.E. Innovative system designs to optimize performance of ultra-low pressure reverse osmosis membranes. Desalination, 118, 63-71, 1998. Ng, H.Y., T.W. Tan, and S.L. Ong. Membrane fouling of submerged membrane bioreactors: impact of mean cell residence time and the contributing factors. Environ. Sci. Technol., 40, 2706-2713, 2006. Noguera, D.R., N. Araki, and B.E. Rittmann. Soluble microbial products (SMP) in anaerobic chemostats. Biotechnol. Bioeng., 44, 1040-1047, 1994 Norberg, D., S. Hong, J. Taylor, and Y. Zhao. Surface characterization and performation evaluation of commercial fouling resistance low-pressure RO membranes. Desalination, 202, 45-52, 2007. Núñez, C., R. León, J. Guzmán, G. Espín, and G. Soberón-Chávez. Role of Azobobacter vinelandii mucA and mucC gene products in alginate production. J. Bacteriol., 182, 6550-6556, 2000. Nyström, M., K. Ruhomäki, and L. Kaipia. Humic acid as a fouling agent in filtration. Desalination, 106, 79-87, 1996. Ognier, S., C. Wisniewski, and A. Grasmick. Influence of macromolecule adsorption during filtration of a membrane bioreactor mixed liquor suspension. J. Membr. Sci., 209, 27-37, 2002. Park, N., B. Kwon, I.S. Kim, and J. Cho. Biofouling potential of various NF membranes with respect to bacteris and their soluble microbial products (SMP): Characterizations, flux decline, and transport parameters. J. Membr. Sci., 258, 43-54, 2005. Painter, H.A. Organic compound in solution in sewage effluents. Chem. & Ind., September, 818-822, 1973. Public Utility Board. Annual Report, 2007/2008. Rautenbach, R., T. Linn, and L. Eilers. Treatment of severely contaminated waste water by a combination of RO, high–pressure RO and NF—potential and limits of the process. J. Membr. Sci., 174, 231-241, 2000. Rebhum, M., and Manka, J. Classification of organics in secondary effluents. Environ. Sci. Techol., 5, 606-609, 1971. 165 References Sablani, S.S., M.F.A. Goosen, R. Al-Relushi, and M. Wilf. Concentration polarization in ultratfiltration and reverse osmosis: a critical review. Desalination, 141, 269-289, 2001. Salgın, S., S. Takaç, and T.H. Özdamar. Adsorption of bovine serum albumin on polyether sulfone ultrafiltration membranes: Determination of interfacial interaction energy and effective diffusion coefficient. J. Membr. Sci., 278, 251-260, 2006. Schiener, P., S. Nachaiyasit, and D.C. Stuckey. Production of soluble microbial products (SMP) in an anaerobic baffled reactor: composition, biodegradability and the effect of process parameters. Environ. Tech., 19, 391-400, 1998. Schneider, R.P., L.M. Ferreira, P. Binder, and J.R. Ramos. Analysis of foulant layer in all elements of an RO train. J. Membr. Sci., 261, 152-162, 2005. Schneider, R.P., L.M. Ferreira, P. Binder, E.M. Bejarano, K.P. Góes, E. Slongo, C.R. Machado, G.M.Z. Rosa. Dynamics of organic carbon and of bacterial populations in a conventional pretreatment train of a reverse osmosis unit experiencing server biofouling. J. Membr. Sci., 266, 18-29, 2005. Schwinge, J., P.R. Neal, D.E. Wiley, D.F. Fletcher, and A.G. Fane. Spiral wound modules and spacers review and analysis. J. Membr. Sci., 242, 129-153, 2004. Seidel, A., and Elimelech, M. Coupling between chemical and physical interactions in natural organic matter (NOM) fouling of nanofiltration membranes: implications for fouling control. J. Membr. Sci., 203, 245-255, 2002. Shahalam, A.M., A. Al-Harthy, and A. Al-Zawhry. Feed water pretreatment in RO systems: unit processes in the Middle East. Desalination. 150, 235-245, 2002. Simmons, M.J.H., P. Jayaraman, and P.J. Fryer. The effect of temperature and shear rate upon the aggregation of whey protein and its implications for milk fouling. J. Food Eng., 79, 517528, 2007. Soltanieh, M., and Gill, W.N. Review of reverse osmosisi membranes and transport models. Chem. Eng. Commun., 12, 279-363, 1981. Song, L., J.Y. Hu, S.L. Ong, W.J. Ng, M. Elimelech, and M. Wilf. Performance limitation of the full-scale reverse osmosis process. J. Membr. Sci., 214, 239-244, 2003. Song, L., and Tay, K.G. Performance prediction of a long crossflow reverse osmosis membrane channel. J. Membr. Sci., 281, 163-169, 2006. Tang, C.Y., and Leckie, J.O. Membrane independent limiting flux for RO and NF membranes fouled by humic acid. Environ. Sci. Technol., 41, 4767–4773, 2007. Tang, C.Y., Y.-N. Kwon, and J.O. Leckie. The role of foulant-foulant electrostatic interaction on limiting flux for RO and NF membranes during humic acid fouling166 References Theoretical basis, experimental evidence, and AFM interaction force measurement. J. Membr. Sci., 326, 526-532, 2009. Tang, C.Y., Y.-N. Kwon, and J.O. Leckie. Fouling of reverse osmosis and nanofiltrtion by humic acid — effects of solution composition and hydrodynamic conditions. J. Membr. Sci., 290, 86-94, 2007. Tasaka, K., T. katsura, H. Iwahori, and Y. Kamiyama. Analysis of RO elements operated at more than 80 plants in Japan. Desalination. 96, 259-272, 1994. Tay, K.G. Dynamics and characterization of membrane fouling in a long reverse osmosis membrane channel. Ph.D. Thesis, Department of civil engineering, National University of Singapore, 2006. Tay, K.G., and Song, L. A more effective method for fouling characterization in a full-scale reverse osmosis process. Desalination, 177, 95-107, 2005. Thongngam, M., and McClements, D.J. Influence of pH, ionic strength, and Temperature on self-association and Interactions of sodium dodecyl sulfate in the absence and presence of chitosan. Langmuir, 21, 79-86, 2005. Tran-Ha, M.H., V. Santos, and D.E. Wiley. The effect of multivalent cations on membrane-protein interactions during cleaning with CTAB. J. Membr. Sci., 251, 179188, 2005. Trägårdh, G. Membrane cleaning. Desalination, 71, 325-335, 1989. Turan, M. Influence of filtration conditions on the performance of nanofiltration and reverse osmosis membranes in dairy wastewater treatment. Desalination, 170, 83-90, 2004. Vedavyasan, C.V. Combating water shortages with innovative uses of membranes. Desalination, 132, 345347, 2000. Veerman, C., L.M.C. Sagis, J. Heck, and E. van der Linden. Mesostructure of fibrillar bovine serum albumin gels. Int. J. Biol. Macromol., 31, 139-146, 2003. Velasco, C., M. Ouammou, J.I. Calvo, and A. Hernández. Protein fouling in microfiltration: deposition mechanism as a function of pressure for different pH. J. Colloid Interface Sci., 266, 148-152, 2003. Vrijenhoek, E.M., S. Hong, and M. Elimelech. Influence of membrane surface properties on initial rate of colloidal fouling of reverse osmosis and nanofiltration membranes. J. Membr. Sci., 188, 115-128, 2001. Vrouwenvelder, J.S., J.A.M. van Paassen, J.M.C. van Agtmaal, M.C.M. van Loosdrecht, J.C. Kruithof. A critical flux to void biofouling of spiral wound nanofiltration and reverse osmosis membranes: Fact or fiction? J. Membr. Sci., 326, 36-44, 2009. 167 References Wang, B.-J., T.-C. Wei, and Z.-R. Yu. Effect of operating temperature on component distribution of West Indian cherry juice in a microfiltration system. LWT-Food Sci. Technol., 38, 683689, 2005. Wehner, M. A research and demonstration project permit under the new California groundwater recharge regulations. Desalination, 87, 37-52, 1992. Wilbert, M.C., J. Pellegrino, and A. Zydney. Bench-scale testing of surfactantmodified reverse osmosis/nanofiltration membranes. Desalination, 115, 15-32, 1998. Wilf, M. Design consequences of recent improvements in membrane performance. Desalination, 113, 157-163, 1997. Wilf, M., and Alt, S. Application of low fouling RO membrane elements for reclamation of municipal wastewater. Desalination, 132, 1119, 2000. Wilf, M., and Klinko, K. Effective new pretreatment for seawater reserve osmosis systems. Desalination, 117, 323-331, 1998. Xiong, Y.L. Influence of pH and ionic environment on thermal aggregation of whey proteins. J. Agric. Food Chem., 40, 380-384, 1992. Xue, J., X. Huang, and E.M.V. Hoek. Roles of specific ion interactions in seawater RO membrane fouling by alginate acid. Environ. Sci. Technol., 43, 3580-3587, 2009. Yamamura, H., K. Kimura, T. Okajima, H. Tokumoto, and Y. Watanabe. Affinity of functional groups for membrane surfaces: Implications for physically irreversible fouling. Environ. Sci. Technol., 42, 5310-5315, 2008. Ye, Y., P.L. Clech, V. Chen, A.G. Fane, and B. Jefferson. Fouling mechanisms of alginate solutions as model extracellular polymeric substances. Desalination, 175, 720, 2005. Ye, Y., V. Chen, and A.G. Fane. Modeling long-term subcritical filtration of model EPS solutions. Desalination, 191, 318-327, 2006. Yiantsios, S.G., D. Sioutopoulos, and A.J. Karabelas. Colloidal fouling of RO membranes: an overview of key issues and effects to develop improved prediction techniques. Desalination, 183, 257-272, 2005. Yoon, S-H., C-H. Lee, K-J. Kim, and A.G. Fane. Effect of calcium ion on the fouling of nanofilter by humic acid in drinking water production. Wat. Res., 32, 2180-2186, 1998. Zhao, Y., L. Song, and S.L. Ong. Fouling of RO membranes by effluent organic matter (EfOM): Relating major components of EfOM to their characteristic fouling behaviors. J. Membr. Sci., 349,75-82, 2010. 168 References Zhou, W., L. Song, and K.G. Tay. A numerical study on concentration polarization and system performance of spiral wound RO membrane modules. J. Membr. Sci., 271, 38-46, 2006. Zhu, X., and Elimelech, M. Fouling of reverse osmosis membranes by aluminum oxide colloids. J. Environ. Eng., 121, 884-892, 1995. Zydney, A.L. Stagnant film model for concentration polarization in membrane system. J. Membr. Sci., 130, 275-281, 1997. 169 Appendix Appendix A. Relationship between NaCl concentration and conductivity Low range 25 Conductivity (s/cm) 20 15 10 0 10 NaCl conc. (mg/L) 170 Appendix 250 Middle range Conductivity (s/cm) 200 150 100 50 0 20 40 60 80 100 800 1000 NaCl conc. (mg/L) 2000 High range Conductivity (s/cm) 1600 1200 800 400 0 200 400 600 NaCl conc. (mg/L) 171 Appendix 10000 Superhigh range Conductivity (s/cm) 8000 6000 4000 2000 1000 2000 3000 4000 5000 NaCl conc. (mg/L) Range R2 Conversion equation COND(μs/cm) Conc.(mg/L) Conc. =0.4426×COND-0.4556 0.9999 2010 1000~5000 172 [...]... RO membrane cell The behavior of local permeate flux and salt rejection in a long channel RO membrane cell was experimentally investigated using a laboratory-scale 1-m long RO membrane channel Concentration polarization modulus (CP) was calculated to correlate the recovery and concentration polarization The effect of spacers on minimizing concentration polarization formation was also investigated Chapter... Numerically simulated permeate flux and experiential data of alginate fouling in a long RO membrane channel xiv Nomenclature Nomenclature c Solute concentration, mg/L cf Organic foulant concentration in the bulk solution, mg/L cf0 Organic foulant concentration in the feed, mg/L ci Molar concentration of the solute, M cm Salt concentration at the membrane wall, mg/L cp Salt concentration in the permeate,... of figures List of Figures Figure 1.1 A schematic diagram of the research objectives and scope of this study Figure 2.1 Alginate molecular structure: (a) alginate monomers (uronic acids: M vs G The carbon atoms C-2 and C-3 of the mannuronate units are partially acetylated (R= -H or -COCH3), all C-5 carbon atoms carry a carboxylate group that may be partially protonated); (b) macromolecular conformation... Effect of ionic strength, pH, cationic ions, temperature Chemical cleaning (EDTA, SDS, NaOH): Effect of Ca2+ Alginate Chemical cleaning (EDTA, SDS, urea): Effect of concentration, pH and cleaning time Phase II: Organic fouling: Membrane module and operating conditions Long RO membrane channel Concentration polarization Fouling development in long channel: Effect of crossflow velocity and initial flux... polysaccharide and protein fractionated directly from the secondary effluent is still in its infancy stage This is probably attributed to the composition and concentration variability of secondary effluent even from the same wastewater treatment plant and availability of the difficulty of access to highly reliable isolation and fractionation technology as well The fractions of macromolecules in secondary... irrigation (eg., golf courses); - A considerably higher reliability and uniformity of the available water flows Despite the attractive contribution and the increasing acceptance of RO technology, separation process via a semi-permeable membrane is plagued by a critical problem, membrane fouling (Kimura et al., 2004; Lapointe et al., 2005; Mulder, 1996) Membrane fouling is a result of contaminant or foulant... organic components in the secondary effluent in water reclamation, membranes and membrane process, and membrane fouling Discussions will focus mainly on the key issues involved in organic fouling Chapter 3 – Materials and methods This chapter describes the small lab-scale RO membrane cell and a long channel RO membrane cell and their operating conditions used in this study It also describes in detail... feed component using membrane filtration is needed (Hu et al., 2003; Jarusutthirak et al., 2002) Organic fouling is associated with natural organic matters that are present in surface water The widely occurring humic acids in surface water are one of the main organic components causing organic fouling for RO process (Nystrom et al., 1996; Yoon et al., 1997) With the advent of wastewater reclamation, the... pharmaceutical industries (Maruyama et al., 2001; Simmons et al., 2006) Separate in-depth study of polysaccharide and protein fouling of RO membranes is essential for the differences between RO and MF/UF membranes in terms of membrane materials and pore structure, and different fouling mechanisms that require different appropriate fouling mitigation measures At present, the characterization of polysaccharide... channel membrane setup, instead of a test setup that averages the flux over the whole channel, varying local permeate flux due to the variations of local parameters can be determined With a knowledge of the fouling behavior of the feed water along a long channel RO membrane, the experimental results obtained can further improve the existing theoretical work on spatial and temporal development of organic . Behavior and Concentration Polarization in a Long RO Membrane Channel 100 6.1 Calculation of concentration polarization 101 6.2 Variation of permeate flux along the channel 104 6.3 Variation of. (uronic acids: M vs G. The carbon atoms C-2 and C-3 of the mannuronate units are partially acetylated (R= -H or -COCH 3 ), all C-5 carbon atoms carry a carboxylate group that may be partially. EDTA cleaning at different (a) pH (the concentration of EDTA solution was fixed at 1mM); and (b) EDTA concentrations (the pH of EDTA solution was fixed at 4.5). Fouling conditions: sodium alginate