Membrane Flocculation Hybrid System as Pretreatment to Brackish and Seawater Reverse Osmosis Desalination System: Emphasis on Chemical Use Reduction and Recovery Centre for Technology in Water and Wastewater (CTWW), School of Civil & Environmental Engineering, Faculty of Engineering & Information Technology (FEIT), University of Technology Sydney (UTS), Sydney, Australia. (E-mail: [email protected]) Fouling is a significant problem in seawater reverse osmosis (SWRO) desalination process. It increases operational and water production costs due to frequent chemical cleaning. It is important to eliminate organic and bio-fouling by pretreatment before passing through SWRO. The conventional pre-treatment systems cannot alleviate organic and bio-fouling which are the major issues in SWRO operation. This project establishes and evaluates a novel submerged membrane flocculation hybrid system (SMFHS) as a cost-effective pre-treatment to SWRO. The emphasis of this project is to reduce the use of chemical and flocculated sludge disposal through the selection of alternative chemicals, pre-adsorption and resource recovery from chemical sludge. Submerged membrane flocculation hybrid system (SMFHS) with GAC pre-adsorption* In the SMFHS set-up, submerged-type of hollow fiber microfiltration (MF) membrane (Cleanfils-S, Polysulfone, Polyethersulfone, Polyvinylidenefluoride (PVDF) of pore size 0.1 µm) was used. The combined effective surface area of MF was 0.1m2. Flocculants were dosed in-line flocculation system. GAC *Granular activated carbon (GAC) filter was operated in adsorption mode at a constant filtration rate of 10 m/h (at a down-flow mode). This was to reduce the use of flocculant (chemical). - S. Jeong, T.V. Nguyen, S. Vigneswaran. (2011) Submerged membrane coagulation hybrid system as pretreatment to organic matter removal from seawater. Water Science and Technology: Water Supply 11(3): 352-357. Modelling of fouling and DOC removal Advanced analytical methods Organic and biological foulants and membrane autopsy were made using following methods: Organic characterisation: Detailed organic fractionation: Liquid Chromatography-Organic Carbon Detector (LC-OCD), XAD resin Molecular weight distribution: High Pressure Size Exclusion Chromatography (HPSEC) Quantification of humic-like, fulvic-like and protein-like organic foulants: Three DimensionFluorescence Excitation Emission Matrix (3D-FEEM) Biopolymeric organic foulant analysis: Transparent exopolymeric particles (TEP) and extracellular polymeric substance (EPS) Bio-available organic fraction of dissolved organic carbon and biofouling potential: Assimilable organic carbon (AOC) Structural study of organic matter: Nuclear magnetic resonance (1H-NMR), Pyrolysis-gas chromatography–mass spectrometry(Py-GC/MS) and Liquid Chromatography–Mass Spectrometry-Ion Trap-Time Of Flight (LC/MS-IT-TOF). Biological foulants: Total direct cell (TDC) count, cell viability and biomass activity (adenosine tri-phosphate; ATP). The fouled membrane analysis: Environmental Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM-EDS), Attenuated Total Reflection-Fourier Transform Infrared spectrometry (ATR-FTIR), Zeta-potential measurement, Atomic Force Microscopy (AFM), and Contact Angle measurement. - S. Jeong, S.-J. Kim, C.M. Kim, S. Vigneswaran, T.V. Nguyen, H.K. Shon, J. Kandasamy, I.S. Kim. (2013) A detailed organic matter characterization of pretreated seawater using low-pressure microfiltration hybrid systems. Journal of Membrane Science 428: 290-300. - S. Jeong, S.-J. Kim, L.H. Kim, M.S. Shin, S. Vigneswaran, T.V. Nguyen, I.S. Kim. (2013) Foulant analysis of a reverse osmosis membrane used pretreated seawater. Journal of Membrane Science 428: 434–444.. Effect of different flocculants - Cake formation was the predominant fouling mechanisms causing fouling in SMFHS - An initial modelling for DOC removal was made using conceptual method Pore blockage Pore constriction The removal occurred by adsorption of un-dissociated compounds onto ferric hydroxide was formulated. DOCremaining (final DOC after coagulant is dosed into the water) can be calculated using the following formula: DOCremaining = DOC0-HAs-BOHs-HBnps. Cake filtration - S. Jeong, Y.J. Choi, T.V. Nguyen, S. Vigneswaran, T.M. Hwang. (2012) Submerged membrane hybrid systems as pretreatment in seawater reverse osmosis (SWRO): Optimization and fouling mechanism determination. Journal of Membrane Science 411–412: 173– 181. - S. Jeong, A. Sathasivan, G. Kastl, W.G. Shim, S Vigneswaran. (2014) Experimental investigation and modeling of dissolved organic carbon removal by coagulation from seawater. Chemosphere 95: 310-316. Economic analysis FeCl3 PFS Al2(SO4)3 PACl TiCl4 Optimal dose (mg/L) 3.0 2.0 3.0 2.0 2.0 Flocculant price (AU$/ton) 200 180 200 260 Flocculant required (ton/d) 0.145 0.167 0.190 Cost of flocculant (AU$/d) 29.1 30.0 Sludge production (ton/d) 0.280 0.250 Sludge treatment price PFS Al2(SO4)3 PACl TiCl4 Optimal dose (mg/L) 1.0 1.0 1.0 1.0 1.0 1,950 Flocculant price (AU$/ton) 200 180 200 260 1,950 0.126 0.079 Flocculant required (ton/d) 0.048 0.083 0.063 0.063 0.040 38.0 32.7 154.5 Cost of flocculant (AU$/d) 9.7 15.0 12.7 16.4 77.3 0.350 0.230 0.200 Sludge production (ton/d) 0.200 0.180 0.230 0.160 0.200 37 37 37 37 37 (AU$/ton) Cost of sludge treatment (AU$/d) Incineration (AU$/d) 37 37 7.4 6.7 8.5 5.9 - Incineration (AU$/d) - - - - +6.6 By-product (AU$/d) - - - - -90.0 GAC operation* (AU$/d) 13.5 13.5 13.5 13.5 13.5 Total cost (AU$/d) 30.6 35.2 34.7 35.8 7.4 Cost saving (AU$/d) 9.9 5.0 17.8 6.3 35.9 37 37 37 (AU$/ton) Cost of sludge treatment (AU$/d) 10.4 9.3 13.0 8.5 - - - - - 8.8 By-product (AU$/d) - - - - -120 Total cost (AU$/d) 39.5 39.3 51.0 41.2 43.3 Preadsorption by GAC filter will help to reduce the operational cost through reduction of the amount of flocculant needed as well as decreased the need of sludge treatment. The cost for treatment of a cubic meter of seawater can reduce from 39.3-51.0 US$/d to 7.4-35.2 US$/d based on 10,000m3/d plant. - T.V. Nguyen, S. Jeong, T.T.N. Pham, J. Kandasamy, S. Vigneswaran. (2014) Effect of granular activated carbon filter on the subsequent flocculation in seawater treatment. Desalination 354: 9-16. Conclusions - S. Jeong, F. Nateghi, T.V. Nguyen, S. Vigneswaran, T.A. Tu. (2011) Pretreatment for seawater desalination by flocculation: Performance of modified poly ferric silicate (PFSi-δ) and ferric chloride as flocculants. Desalination 283: 106–110. - S. Jeong, Y. Okour, T.V. Nguyen, H.K. Shon, S. Vigneswaran. (2013) Ti-salt flocculation for dissolved organic matter removal in seawater. Desalination and Water Treatment 51(16-18): 3591-3596. RO testing FeCl3 Sludge treatment price - DOC removal efficiency as a function of concentrations of five different flocculants (initial organic matter concentration of seawater was 1.41 mg/L) The chemical dose necessary with poly ferric sulphate (PFS) and poly aluminium chloride (PACl) was minimal at 2 mg/L. Alum produced the highest amount of chemical sludge. This amount was 30% more than that with other flocculants. Although, TiCl4 was costly chemical, the TiO2 production from the TiCl4 sludge makes it cost-effective. The results from LC-OCD showed that most of hydrophobic organic compounds removed and more than 35% of hydrophilic substances such as humic (molecular weight 1000 Da) reduced significantly. SMFHS with GAC pre-adsorption removed organic compounds in the seawater. As a result, it helped to reduce the flux decline in RO and organic fouling on the RO membrane. The reduction of organic, especially the LMW organics and AOC compounds on the RO membrane resulted in the a lower biofouling of RO membrane. The addition of GAC preadsorption also helped to reduce significantly the dose of flocculants required for organic removal. An energy efficient, compact submerged membrane flocculation hybrid pre-treatment system to reduce the organic fouling to RO!! This project led to novel and practical outcomes for RO desalination. (1) It resulted in an energy efficient, compact submerged membrane flocculation hybrid pre-treatment system to reduce the organic fouling to RO. The alleviation of membrane fouling will reduce the operational cost of RO. The system proposed in this study alleviated the fouling problems and made the small-scale desalination process attractive. (2) This project reduced the use of chemical usage and subsequent sludge production through the use of alternative chemicals, and effective additional pre-treatment such as pre-adsorption. Recovery of TiO2 from Tisalt based coagulant sludge reduced the amount of sludge discharged. Alternative polymeric inorganic flocculants with and without pre-adsorption reduced the chemical usage and sludge production while achieving superior organic removal. The proposed alternative Ti-salt coagulant significantly reduced the sludge by recovery of TiO2. Acknowledgement This study was supported by the National Centre of Excellence in Desalination (NCED) which is funded by the Australian Government through the Water for the Future initiative.
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