Reverse Draw Solute Permeation in Forwar20160427-15782-1dyzc83

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Article
High Performance Forward Osmosis Membranes Used
for Treating High Salinity Oil-bearing Wastewater
Shanshan Xu, Pengfei Lin, Xiaochan An, Yunxia Hu, Zhenbo Wang, Like Zhong, and Qingshan Niu
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b02917 • Publication Date (Web): 09 Oct 2017
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Page 1 of 46 Industrial & Engineering Chemistry Research
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High Performance Forward Osmosis Membranes Used
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for Treating High Salinity Oil-bearing Wastewater
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13 Shanshan Xu a, Pengfei Lin a,*, Xiaochan An b, c, Yunxia Hu b, c, Zhenbo Wang a, Like Zhong a, Qingshan
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15 Niu a
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18 a
College of Chemical Engineering, China University of Petroleum (East China), Qingdao, Shandong
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21 Province 266580, P.R. China
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b
24 State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic
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27 University, Tianjin 300387, P.R. China
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29 c CAS Key Laboratory of Coastal Environmental Processes and Ecological Remediation; Yantai
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32 Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai, Shandong Province 264003,
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35 P.R. China
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41 ABSTRACT: Forward osmosis (FO), an emerging osmotic driving membrane separation
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43 process, can be directly used in high salinity oil-bearing (HSOB) wastewater treatment. In
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46 this study, the thin film composite (TFC) polyamide FO membranes were fabricated for
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49 HSOB wastewater treatment. The impacts of the draw solution (DS) concentration, cross-
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52 flow rate, stirring rate and the membrane orientation on membrane performances were
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55 researched. The results indicated that the FO operation mode was better to achieve a stable
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57 water flux of TFC membranes as 29 L/m2·h under 15 cm/s cross-flow rate and 3 M NaCl
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Industrial & Engineering Chemistry Research Page 2 of 46
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4 as the DS, which was 61% higher than the water flux in the un-optimized operating
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7 conditions (18 L/m2∙h). The rejection rate of salt and oil was 99% and 96%. Additionally,
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10 the effect of different oil concentrations of HSOB wastewater was studied and the results
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13 showed that FO performed well to treat HSOB wastewater when the oil concentration was
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less than 700 mg/L.
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18 KEYWORDS: Forward Osmosis; TFC Polyamide Membrane; High Salinity Oil-bearing
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21 Wastewater; Oil Concentration
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4 1. INTRODUCTION
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7 In the process of oil exploitation and refining, a large amount of high salinity oil-
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10 bearing (HSOB) wastewater is produced.1 HSOB wastewater has a complex composition,
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13 containing a variety of salts, solid particles, dissolved gas, oil slurry and other organic
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substances, so the wastewater has high viscosity, salinity, and is difficult to treat.2,3
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18 Discharging HSOB wastewater can not only cause environmental pollution, health hazards,
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21 and ecological harm, but also waste water resources and polymers.4 In addition, minerals
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24 in oilfield produced water lead to the viscosity decrease of polymer flooding water, which
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27 lower the oil displacement efficiency significantly.5 If HSOB wastewater is to be reused, it
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is necessary to remove the pollutants especially the minerals. The treatment of HSOB
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32 wastewater has become an important issue.
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35 Conventional treatment technologies for HSOB wastewater include hydrocyclone,
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38 gas flotation, reverse osmosis (RO), and multi-effect evaporation crystallization.1,6
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41 However, there were many problems such as complex equipment, a large footprint, high
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43 cost, incomplete treatment, and the secondary pollution of these technologies.7-9 Therefore,
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46 it is important to find energy efficient, economical and reliable treatment technologies for
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49 HSOB wastewater.
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52 Forward osmosis (FO) is an emerging separation process, which depends on the
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55 osmotic pressure to drive the water in a feed solution (FS) into a higher concentrated draw
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57 solution (DS) through a FO membrane.10 The process makes the osmotic pressure
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4 difference between the FS and the DS as the driving force, which can address several
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7 shortcomings of traditional pressure-driven membrane processes, such as high operating
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10 pressure, high power consumption, sophisticated membrane modules and high operation
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13 and maintenance costs.11 Although FO may not considerably reduce energy consumption,
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it will be excellent in those scenarios in which RO is limited, such as highly contaminated
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18 wastewater treatment.12 FO can be directly applied to the reuse of high salt organic
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21 wastewater, advanced treatment of dyeing wastewater, and landfill leachates, which can
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24 effectively reduce costs and shorten the treatment process.13-15 Compared with RO
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27 processes, FO is a green separation process with lower membrane fouling, lower cost of
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fouling removal and less chemical cleaning agents.16,17 FO can effectively reduce the
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32 volume of wastewater in high concentrations and the follow-up treatment costs, especially
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35 hybrid FO systems have been used in oily wastewater treatment with the potential to
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38 achieve wastewater zero discharge.10,13,18
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41 In FO process, the diluted DS can be recovered and utilized by heating,
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43 electromagnetic separation, ultrafiltration (UF), nanofiltration (NF) and RO technology,19
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46 while the concentrated HSOB wastewater can be treated by evaporation crystallization.18
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49 The whole process realized recycling and wastewater zero discharge, which has important
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52 environmental protection and economic significance.
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55 In order to efficiently treat HSOB wastewater, this study focused on the research as
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4 evaluating and characterizing the membrane properties, (2) studying the impact of different
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7 operating parameters of HSOB wastewater treatment by FO technology to optimize the
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10 experimental conditions, and (3) evaluating the effect of FO technology on HSOB
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13 wastewater treatment, the rejection rate of oil and salt pollutants, and oil concentration
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range.
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18 2. MATERIALS AND METHODS
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21 2.1 Materials
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24 The chemical agents used throughout this study, such as NaHCO3, NaCl, NaSO4,
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27 K2CO3, CaCl2 and MgCl2, were of analytical reagent (AR) grade purchased from Sinopham
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Chemical Reagent Co., Ltd, China. Deionized water (DI) (specific resistance, ≥10 MΩ·cm)
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32 was produced in the laboratory. Dimethyl silicone oil was purchased from West Long
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35 Chemical Co., Ltd, (China), of which the relative density at 20 ℃ was 0.965-0.973 g/ml
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38 and the viscosity was 330-370 mm2/s. Emulsifier (Tween 80, chemically pure) was
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41 purchased from Sinopham Chemical Reagent Co., Ltd, China. Polysulfone (PSF, Udel P-
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43 3500) was purchased from Solvay Advanced Polymers (Brussels, Belgium). N-methyl-2-
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46 pyrrolidinone (NMP, anhydrous, 99.5%), 1, 3-phenylenediamine (MPD, >99%), and 1, 3,
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49 5-benzenetricarbonyl trichloride (TMC, 98%) were acquired from Sigma Aldrich (St.
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52 Louis, MO, USA). Hexane was obtained from Sinopharm Chemical Reagent Beijing Co.,
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55 Ltd, (China). All chemicals were used as received.
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4 2.2 Source water
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7 Based on water quality indexes of polymer contained produced water of the Daqing
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10 oilfield in Heilongjiang Province, which is the biggest oilfield in China, the artificial HSOB
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13 wastewater was prepared in the laboratory. The water quality indicators are shown in Table
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1.20
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18 Table 1. Water quality indicators (Unit: mg/L)
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21 Items Values
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24 K+, Na+ 1329.62
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27 Ca2+ 34.07
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30 Mg2+ 17.02
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Cl- 797.85
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35 SO42- 187.32
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38 HCO3- 1952.64
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41 CO32- 60.02
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44 Salinity 4378.54
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46 Suspended solids 15.80
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49 Oil 15.50
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52 The artifical water sample was prepared by adding 21.5098 g NaHCO3, 8.66 g NaCl,
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55 2.2166 g NaSO4, 1.1044 g K2CO3, 0.7564 g CaCl2 and 0.8614 g MgCl2 to 8 L DI water
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58 and mixing well. The mineralization degree of produced water was simulated. Then 20 ml
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4 emulsifier (1 g/L) were added to 124 mg dimethyl silicone oil to mix well, gradually added
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7 the above prepared high salinity wastewater and stirred at 3500 r/min for 20 min by high
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10 shearing dispersion emulsifying machine (DE-100L, Nantong Clare Mixing Equipment
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13 Co., Ltd, China) to prepare HSOB wastewater.21 The pH of the artificial HSOB wastewater
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was 9.25.
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18 2.3 Draw solution
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21 DS is one of the most important factors controlling FO process, so the selection of an
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24 appropriate DS is vital for processing efficiency. A variety of draw solutes have been
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27 developed in the past few decades, which are divided into inorganic DS, organic DS and
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other DS.22 At present, inorganic DS is the most widely used in FO because of small
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32 molecular weight (wt), high solubility and osmotic pressure, which has great potential in
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35 HSOB wastewater treatment and wastewater zero discharge.23,24
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38 NaCl solution has high solubility, high osmotic pressure, and relatively cheap.
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41 Especially in the coastal areas, seawater can be directly used as DS, which is conducive to
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43 the promotion and application of FO technology. Although reverse salt flux of NaCl DS is
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46 higher, considering the osmotic pressure and cost of the DS, NaCl solution is selected as
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49 the DS for the treatment of HSOB wastewater in this paper. The diluted NaCl DS is
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52 recovered and utilized by RO technology. A commercially DowTM UHP RO membrane was
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55 acquired from The Dow Chemical Company (China).
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4 2.4 Fabrication of FO membrane
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7 FO membranes used in HSOB wastewater treatment are mainly cellulose triacetate
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10 (CTA) membranes and thin film composite (TFC) membranes. Compared with CTA
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13 membranes, TFC membranes has higher water flux, lower reverse salt flux, more selective,
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wider range of PH, better chemical stability and mechanical strength.15,25,26 Considering
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18 the membrane materials, process characteristics and properties of HSOB wastewater, TFC
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21 polyamide FO membranes were prepared.
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24 Fabrication of TFC FO membranes involved two steps. First, the PSF support
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27 membrane was fabricated by non-solvent-induced phase separation (NIPS). Second, a
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polyamide active layer was formed on the polysulfone support membrane via interfacial
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32 polymerization, following the reported procedure.25 PSF beads were dissolved in NMP
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35 with stirring for 6 h at room temperature to obtain 12 wt % homogenous casting solution,
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38 which was then degassed in a desiccator for at least 12 h. A steel casting knife was used to
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41 cast the PSF solution with 150 μm gate heights onto the NMP pre-wetted polyethylene
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43 terephthalate (PET) nonwoven fabric. Upon immersion in a water coagulation bath for 10
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46 min at room temperature, the white PSF support membrane was formed, and transferred to
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49 deionized water for storage. During the casting process, the relative humidity (RH) was set
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52 at 40±5 RH % in a clean room.
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55 To form the polyamide active layer on the PSF support membrane, the top selective
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57 side of the wet PSF support membrane was immersed in 3.4 wt % MPD aqueous solution
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4 for 2 min. Next the excess MPD was removed from the membrane surface using a rubber
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7 roller, the polysulfone support membrane containing MPD was then immersed in a 0.15
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10 wt % TMC hexane solution for 60 s to form the polyamide active layer, and cured in
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13 deionized water at 95 °C for 120 s. Finally, the TFC membrane was thoroughly rinsed and
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stored in deionized water at 4 °C. Key characteristics of the TFC FO membranes are
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18 measured and shown in Table 2.
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21 Table 2. Properties of fabricated TFC FO membranes
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24 Water permeability A a NaCl permeability B b NaCl rejection R b PH Thickness
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27 L/(m2hbar) L/(m2h) % μm
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30 TFC 1.26 0.17 98.4 2-11 92
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by RO using 50 mM NaCl as feed solution at pressure of 13.8 bar (200 psi).
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38 2.5 Evaluation of FO membranes properties
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41 A laboratory-scale FO system which equipped with a cross-flow membrane cell was
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44 used to determine water flux and reverse salt flux across the membrane. Two peristaltic
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47 pumps (BT600-2J, Longer Pump Co., Ltd., China) were used to provide power to achieve
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49 cycle circulation. The flow chart of the FO membrane set-up is shown in Figure 1.
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24 Figure 1. Flow chart of the FO membrane set-up
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27 The cross-flow velocity between the DS and FS was adapted by the peristaltic pump.
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DI water and HSOB wastewater were used as the FS, and NaCl solution was used as the
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32 DS. Water in the FS was driven into the DS through the FO membrane under the natural
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35 osmotic pressure, so that the FS was concentrated, and the DS was diluted. The operating
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38 temperature was 25 ℃, and the operating pressure was atmospheric pressure. The water
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41 flux and reverse salt flux was respectively calculated through the detected data of the
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43 electronic analytical balance (ME203/02, Mettler Toledo Instruments (Shanghai) Co., Ltd.,
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46 China) and electrical conductivity meter (DDS-11AW, Shanghai Bante Instruments
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49 Limited, China) every 20 min. The oil concentration of the FS and DS was measured by
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52 total organic carbon (TOC) tester (TOC-L, Shimadzu Co., Ltd., Japan) after dilution of the
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55 DS 10 times to ensure accurate results in high salinity conditions. Each experiment ran for
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57 120 min to ensure stable and comparable membrane flux while saving time and operating
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4 costs. The experimental process was closed and conformed to the law of conservation of
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7 mass. FO membrane was backwashed with DI water for 30 min after each experiment to
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10 keep it clean. Experimental errors were all less than 6%.
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13 Water flux Jw (L/m2·h) is the water volume through the FO membrane per unit time
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per unit membrane area, which can be calculated by equation 1.27
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18 ∆𝑚
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𝐽𝑤 = (1)
𝜌𝐴𝛥𝑡
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Where Δm (g) is the weight of water that permeates across the FO membrane in a
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24 predetermined time Δt (h) (20 min), ρ (kg/m3) is the density of water, and A (m2) is the
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27 effective area of the membrane.
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30 Different concentrations of solution on both sides of the membrane resulted in the
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33 solute diffusion from the DS to the FS, which can reduce the FO efficiency. In unit time t
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36 and unit effective membrane area A, the amount of the solute that diffuses from the DS to
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39 the FS is reverse salt flux, which is calculated as follows.27
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41 𝐶𝑡 𝑉𝑡 − 𝐶0 𝑉0
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43 𝐴∆𝑡
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45 Where C0 (mol/L) and V0 (L) are the salt concentration and the volume of the FS at
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48 the beginning of the time interval, respectively, while Ct (mol/L) and Vt (L) are the salt
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51 concentration and the volume of the FS at time t during the FO tests, respectively. JS
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(mol/m2·h) is the reverse salt flux.
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4 flux, which is determined by the membrane active layer and can intuitively characterize
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7 the membrane property.28 JRFS (L/mol) is calculated by equation 3.
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𝑅𝑠 = (1 − ) × 100% (4)
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Where CDS is the initial concentration of the DS.
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25 concentration of the FS and DS by equation 5.30
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28 𝐶𝑠(𝑡)
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𝐶𝑓(𝑡)
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32 Where Cs(t) (mg/L) is the actual permeate concentration of the TOC in the DS at t time,
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35 and Cf(t) (mg/L) is the concentration of the TOC in the FS at t time.
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38 3. RESULTS AND DISCUSSION
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3.1 FO membrane performance
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43 3.1.1 Membrane characterization
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46 The cross-sectional image and the dense surface layer image of the TFC membranes
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49 were detected by a scanning electron microscope (SEM) (Phenom G3, Phenom Scientific
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52 Instrument (Shanghai) Co., Ltd., China). Membrane samples were dried in a vacuum
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condition and fractured in liquid nitrogen. Then samples were sputtered gold before SEM
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57 imaging. SEM images are shown as Figure 2.
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18 Figure 2. SEM images of the TFC FO membranes: (a) porous layer cross-sectional micrograph, (b) top
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21 view of dense surface layer.
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24 As shown in Figure 2, the TFC FO membrane was composed of a polyamide active
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27 layer (AL) formed by interfacial polymerization and a porous ultrafiltration support
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membrane. The polyamide surface presents a characteristic uniform ridge-and-valley
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32 morphology, shown in Figure 2b. The porous layer consisted of sponge-like pores and
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35 finger-like pores, shown in Figure 2a. The finger-like pore structure ensured that the
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38 membrane had not only high water flux, but also a low degree of internal concentration
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41 polarization (ICP).31 At the same time, the non-woven fabric with high toughness and good
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43 mechanical properties was used as a support material, and its network structure gave good
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46 support for the active layer.
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49 The surface roughness of the TFC membranes was evaluated using an atomic force
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52 microscope (AFM) (SPM-9700, Shimadzu Co., Ltd., Japan). Membrane samples were
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55 dried in a vacuum condition and then smoothly pasted on the AFM. Generally, the ratio of
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57 average roughness Ra to the root mean squared roughness Rq represents the membrane
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4 surface smoothness. The smaller the values of Ra/Rq obtained, the smoother the membrane
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7 surface is and the better the antifouling property of the membrane is.32-34 The Ra/Rq value
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10 of the TFC membranes was 0.77 which less than the CTA membranes Ra/Rq=0.7926 and the
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13 antifouling property of the TFC FO membranes was good.
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The contact angle reflects the hydrophilicity of the membrane, and the smaller the
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18 contact angle, the stronger the hydrophilicity of the membrane.35 The contact angle was
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21 measured by the contact angle measurement instrument (SD200C, Solon (Shanghai)
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24 information technology Co., Ltd., China). Membrane samples were dried in a vacuum
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27 condition and then smoothly pasted on the slide. 10 μL DI water droplets were dropped on
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the membrane surface and the contact angle was observed after 5 s. The experiment was
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32 repeated 8 times to get the average value of the contact angle. The average contact angle
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35 was 30°, which was less than 90°, so the TFC FO membranes had a strong hydrophilic
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38 property.
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41 3.1.2 Water flux and reverse salt flux
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43 The water flux and reverse salt flux of the TFC FO membranes were evaluated using
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46 2 M NaCl DS under a 15 cm/s cross-flow velocity while the AL towards the FS (FO mode).
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49 DI water and HSOB wastewater were as the FS respectively, and the oil concentration of
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52 HSOB wastewater was 15.5 mg/L. The temperature was maintained at 25 °C and the
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55 pressure was atmospheric pressure. The results are shown as Figure 3.
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5 35
6 (a)
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Water flux (L/m2h)

8 25
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12 10
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14 5 DI water
High salinity oil-bearing wastewater
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16 20 40 60 80 100 120
17 Time (min)
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20 1.4
21 DI water
1.2 (b)
22 High salinity oil-bearing wastewater
Reverse salt flux (mol/m2h)
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25 0.8
26 0.6
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31 0.0
20 40 60 80 100 120
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Time (min)
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35 Figure 3. The long-term water flux (a) and reverse salt flux (b) of the TFC FO membranes used for
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38 treating HSOB wastewater (2 M NaCl solution as the DS, DI water and HSOB wastewater as the FS,
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41 cross-flow rate of 15 cm/s, FO mode, 25 °C).
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43 As shown in Figure 3a, the water flux both reduced because of the decreased osmotic
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46 pressure and the increased concentration polarization during the separation process. The
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49 measured average DI water flux was 21 L/m2∙h, and the average water flux with HSOB
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52 wastewater as the FS was 18 L/m2∙h, which lower than that with the DI water. This was
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55 due to lower osmotic pressure difference between the FS and the DS to decrease the driving
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57 force and higher boundary layer resistance on the FS side due to higher viscosity of HSOB
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4 wastewater.36 The water flux with HSOB wastewater as the FS reduced faster with
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7 increased running time which may be attributed to three points. Oil increased the viscosity
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10 of HSOB wastewater and the boundary layer resistance, which resulted in the feed solute
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13 accumulation on the membrane surface during FO process, and reverse draw solute also
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increased the solute concentration on membrane surface that was much higher than its
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18 concentration in the main body of the FS, this caused more severe external concentration
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21 polarization (ECP).37,38 Meanwhile, higher reverse salt flux (Figure 3b) led to Na+ and Cl-
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24 more likely to accumulate in the porous layer of the TFC membrane to exacerbate ICP. 26
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27 Furthermore, oil and salts in HSOB wastewater were inevitably penetrated into the DS
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through the membrane. The oil not only caused the organic fouling of the membrane, but
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32 also increased the mass transfer resistance of the membrane, so that the salt ions were easier
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35 to crystallize around the membrane pores to cause membrane fouling and greatly decreased
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38 water flux.39,40
39
40
41 Reverse salt flux was measured and it was found to be higher when HSOB wastewater
42
43 as the FS (Figure 3b). For the same draw solute, reverse solute flux is mainly proportional
44
45
46 to the effective concentration difference on both sides of the membrane active layer, and
47
48
49 theoretically the effective concentration difference with DI water as the FS is larger than
50
51
52 that with HSOB wastewater as the FS. However, the flow direction of water molecules in
53
54
55 the FS and solute molecules in the DS in the membrane is reversed. The higher water flux
56
57 hindered the reverse solute flux, which led to lower reverse salt flux with DI water as the
58
59
16
60
1
2
3
4 FS.41 Furthermore, Arena et al.42 and Coday et al.40 found that ion rejection decreased with
5
6
7 decreasing osmotic pressure for TFC membranes to increase the reverse salt flux, and the
8
9
10 presence of cations in the FS would promote the reverse diffusion of the cations in the DS
11
12
13 through the TFC FO membranes to increase the reverse salt flux. This may be one of the
14
15
reasons why HSOB wastewater as the FS has higher reverse salt flux. Reverse salt flux of
16
17
18 both first increased and then remained stable. Because initial high water flux hindered the
19
20
21 reverse salt flux, and then both the water flux and the concentration difference between the
22
23
24 DS and FS gradually reduced which resulted in stable reverse salt flux.
25
26
27 3.2 Optimization of operating parameters
28
29
The factors that influence the FO membrane properties mainly included the membrane
30
31
32 material, membrane structure, and the operating parameters such as the DS, cross-flow
33
34
35 velocity, and membrane orientation.43 The effects of the concentration of the DS, the cross-
36
37
38 flow rate, the stirring rate and the membrane orientation on HSOB wastewater treatment
39
40
41 were evaluated to optimize the operating parameters.
42
43 3.2.1 Effect of draw solution concentration
44
45
46 The concentration of the DS has an important effect on the water flux. The osmotic
47
48
49 pressure determines the driving force in the FO process and is directly related to the
50
51
52 concentration of the DS.44 Therefore, the effect of different concentrations of the DS on
53
54
55 HSOB wastewater treatment was studied to identify the optimum concentration.
56
57 HSOB wastewater was used as the FS, and 1 M, 2 M, 3 M and 4 M NaCl solutions
58
59
17
60
1
2
3
4 were used as the DS in order to study the water flux and reverse salt flux of the FO
5
6
7 membrane (i.e., oil concentration of 15.5 mg/L, cross-flow rate of 15 cm/s, FO mode,
8
9
10 25 °C). The results are shown in Figure 4.
11
12
13 40
14 (a) 1M NaCl
35 2M NaCl
15
3M NaCl
16 30
4M NaCl
17 25
18
20
19
20 15
21 10
22
5
23
24 0
20 40 60 80 100 120
25
Time (min)
26
27
28
2.0
29
(b)
30
31 1.5 1.26
32
33 0.98
0.83
34 1.0
35 0.54
36
0.5
37
38
39 0.0
40 1 2 3 4
41 DS concentration (M)
42
43 Figure 4. The water flux (a) and reverse salt flux (b) of the TFC FO membranes under different DS
44
45
46 concentrations (1 M, 2 M, 3 M and 4 M NaCl solutions as the DS, HSOB wastewater as the FS, cross-
47
48
49 flow rate of 15 cm/s, FO mode, 25 °C).
50
51
52 As shown in Figure 4a, the water flux decreased with increased time due to decreased
53
54
55 osmotic pressure, increased concentration polarization and membrane fouling as described
56
57 in section 3.1.2. The average water flux at the DS concentrations of 1 M, 2 M, 3 M, 4 M
58
59
18
60
1
2
3
4 was 13.72 L/m2∙h, 17.77 L/m2∙h, 23.18 L/m2∙h, 23.50 L/m2∙h, which increment was 4.05
5
6
7 L/m2∙h, 5.41 L/m2∙h, 0.32 L/m2∙h. The water flux increased with increased DS
8
9
10 concentration because of increased osmotic pressure as the driving force. However, the
11
12
13 water flux increment was greatly reduced when the concentration of the DS was more than
14
15
3 M. This was mainly attributed to the increased DS concentration difference resulted to
16
17
18 increased reverse salt flux (Figure 4b), which enhanced the concentration polarization and
19
20
21 membrane fouling.45 Specially, higher DS concentration accelerated the DS consumption
22
23
24 and increased the operating costs. Furthermore, as shown in Figure 4b, the increment of
25
26
27 the average reverse salt flux was small when the concentration of the DS was 3 M. This
28
29
due to the higher water flux hindered the reverse solute flux as described in section 3.1.2.
30
31
32 Therefore, a 3 M NaCl solution as the DS was better.
33
34
35 3.2.2 Effect of the cross-flow velocity
36
37
38 The DS and the FS flow through both sides of the membrane in cross-flow mode. The
39
40
41 cross-flow rate influences the water flux of the membrane. Generally, the water flux
42
43 increases with increasing cross-flow rate in the RO membrane process.44 The influence of
44
45
46 the cross-flow rate on water flux needs to be explored further.
47
48
49 HSOB wastewater with 15.5 mg/L oil concentration as the FS and 2 M NaCl solution
50
51
52 as the FS were applied to investigate the water flux and the reverse flux selectivity of the
53
54
55 TFC FO membranes at different cross-flow velocities of the DS and FS (i.e., cross-flow
56
57 rates from 9 cm/s to 18 cm/s, FO mode, 25 °C). The results are shown in Figure 5.
58
59
19
60
1
2
3
4
5 50
6 45 (a) 9cm/s
7 40 12cm/s

15cm/s
8 35 18cm/s
9 30
10 25
11 20
12 15
13 10
14 5
15 0
16 20 40 60 80 100 120
17 Time (min)
18
19
20 18
21 (b)
Reverse flux selectivity (L/mol)
16
22 12.73
13.26 12.98
14 12.3
23
12
24
25 10
26 8
27 6
28 4
29
2
30
31 0
9 12 15 18
32
Cross-flow velocity (cm/s)
33
34
35 Figure 5. The water flux (a) and the reverse flux selectivity (b) of the TFC FO membranes at different
36
37
38 cross-flow velocities of the DS and FS (2 M NaCl solution as the DS, HSOB wastewater as the FS,
39
40
41 cross-flow rates of 9 cm/s, 12 cm/s, 15 cm/s, and 18 cm/s, FO mode, 25 °C).
42
43 Figure 5a indicates that the water flux increased with increasing cross-flow velocity,
44
45
46 but the growth trend was relatively small. The reason was that the increasing cross-flow
47
48
49 rate increased the turbulence at the membrane vicinity, which led to the decrease in the
50
51
52 thickness of the ECP layer and the increase of the water flux. However, this phenomenon
53
54
55 has shown a strong influence on ion flux but a low influence on volumetric flux.46,47 And
56
57 the ICP that occurred in the porous support layer was identified to be the main factor for
58
59
20
60
1
2
3
4 water flux reduction of FO membranes, which was not effectively reduced by increasing
5
6
7 the cross-flow rate, so the growth trend of the water flux was relatively small.48 In order to
8
9
10 further clarify the effect of the cross-flow velocity on the membrane property, the reverse
11
12
13 flux selectivity was evaluated (equation 3) as shown in Figure 5b.
14
15
As shown in Figure 5b, the reverse flux selectivity was different under different flow
16
17
18 rates. When cross-flow velocity was 15 cm/s, the reverse flux selectivity was the best. This
19
20
21 was attributed to the fact that the increased cross-flow rate reduced the ECP of the
22
23
24 membrane, which not only increased the water flux but also increased the reverse salt
25
26
27 flux.49 But the difference in the reverse flux selectivity under different cross-flow rates was
28
29
small, which also indicated that increasing the cross-flow rate could reduce the ECP but
30
31
32 had little effect on reducing ICP even to increase operating rate. This shows that it is vital
33
34
35 to select suitable cross-flow rate in FO process.
36
37
38 3.2.3 Effect of the stirring rate on the feed solution side
39
40
41 HSOB wastewater has a high viscosity and easily form a boundary layer resistance to
42
43 reduce water flux in FO process. It is beneficial to study the effect of the stirring rate on
44
45
46 water flux. HSOB wastewater was used as the FS which was stirred by a digital electric
47
48
49 stirrer (JJ-1, Changzhou Jintan Liangyou Instrument Co. Ltd., China), and 2 M NaCl
50
51
52 solution was used as the DS to study the water flux of the TFC FO membranes at different
53
54
55 stirring rate of 0 revolutions (r) /min, 100 r/min, 300 r/min, and 500 r/min on the FS side
56
57 (i.e., oil concentration of 15.5 mg/L, cross-flow rate of 15 cm/s, FO mode, 25 °C). The
58
59
21
60
1
2
3
4 results are shown in Figure 6.
5
6
7 30
8 0 r/min
100 r/min
9 25
300 r/min

10 500 r/min
11 20
12
13 15
14
15 10
16
17 5
18 20 40 60 80 100 120
19 Time (min)
20
21 Figure 6. The water flux of the TFC FO membranes at different stirring rate on the FS side (2 M NaCl
22
23
24 solution as the DS, HSOB wastewater as the FS, stirring rate of 0 r/min, 100 r/min, 300 r/min, and 500
25
26
27 r/min, cross-flow rate of 15 cm/s, FO mode, 25 °C).
28
29
As shown in Figure 6, the average water flux was 15.57 L/m2∙h, 16.79 L/m2∙h, 19.14
30
31
32 L/m2∙h and 17.78 L/m2∙h at the stirring rate of 0 r/min, 100 r/min, 300 r/min and 500 r/min.
33
34
35 The water flux increased with the increased stirring rate which was less than 300 r/min.
36
37
38 This was caused by the increased turbulence to speed up the mixing of the FS and reduce
39
40
41 the viscosity of HSOB wastewater by stirring the FS, which reduced the boundary layer
42
43 resistance and decreased the ECP. But the increase of water flux was not obvious as
44
45
46 described in section 3.2.3. The water flux only increased by 7.83% at the stirring rate of
47
48
49 100 r/min.
50
51
52 However, water flux increased by 22.93% at the stirring rate of 300 r/min while it
53
54
55 decreased rapidly with the increased time. This was attributed to higher stirring rate would
56
57 form bubbly flow, which could generate intense tangential flow along the membrane and
58
59
22
60
1
2
3
4 further decrease the ECP, therefore enhancing the water flux.50 But small bubbles may
5
6
7 coalesce to form big bubbles in the membrane module, which reduced the effective
8
9
10 membrane area and increased the instability of the system, so the water flux reduced rapidly.
11
12
13 When the stirring rate increased to 500 r/min, the flow was more complicated which
14
15
adversely affected water flux and caused higher operating costs. Therefore, it is benefit to
16
17
18 stir the FS with high viscosity and the stirring speed is controlled within 300 r/min.
19
20
21 However, considering the water flux, the stability of FO system and the operation cost, the
22
23
24 FS may not be stirred in this paper.
25
26
27 3.2.4 Effect of membrane orientation
28
29
Two different membrane orientations can be applied in the FO process because of
30
31
32 asymmetric structure of the FO membrane.51 The first orientation is the AL towards the FS,
33
34
35 also known as the FO mode. The second orientation is the AL towards the DS, also known
36
37
38 as the pressure-retarded osmosis (PRO) mode.52
39
40
41 Since there are many differences in membrane performance between the FO mode
42
43 and the PRO mode, the results of water flux in both modes were conducted for comparison
44
45
46 as shown in Figure 7. Experimental conditions were as follows: 2 M NaCl solution as the
47
48
49 DS, HSOB wastewater as the FS, oil concentration of 15.5 mg/L, cross-flow rate of 15
50
51
52 cm/s, 25 °C.
53
54
55
56
57
58
59
23
60
1
2
3
4 35
5
6 30
7

8 25
9
10
20
11
12 FO mode
15
13 PRO mode
14
10
15 20 40 60 80 100 120
16 Time (min)
17
18 Figure 7. The water flux of the TFC FO membranes under different membrane orientations (2 M NaCl
19
20
21 solution as the DS, HSOB wastewater as the FS, cross-flow rate of 15 cm/s, 25 °C).
22
23
24 Figure 7 shows that the initial water flux in the PRO mode was higher than that in the
25
26
27 FO mode, it was due to the fact that the ICP which could reduce the effective driving force
28
29
in the FO mode was more severe than that in the PRO mode. However, the decline of water
30
31
32 flux in the PRO mode was faster than that in the FO mode, which was attributed to the self-
33
34
35 compensation of ICP at the draw side in the FO mode.41,53 On the other hand, contaminants
36
37
38 in the FS readily entered into the porous layer in the PRO mode so as to fill the pores and
39
40
41 results in flux reduction. So the stability of the membrane in the FO mode was better. FO
42
43 membrane orientation has been put forward for the treatment of high fouling feed solutions
44
45
46 such as wastewater effluent.54 The results are similar to those observed for the treatment of
47
48
49 other difficult feed waters in previous FO studies.55-57
50
51
52 3.3 Treatment effect
53
54
55 Through the experimental study of the above on the operating parameters, the
56
57 optimum experimental conditions were established. The water flux and reverse salt flux of
58
59
24
60
1
2
3
4 the TFC FO membrane under 15 cm/s cross-flow velocity were evaluated using 3 M NaCl
5
6
7 solution as the DS and HSOB wastewater with 15.5 mg/L oil concentration as the FS. The
8
9
10 membrane orientation was FO mode, the temperature was maintained at 25 °C, and the
11
12
13 pressure was atmospheric pressure. Each experiment ran for 120 min. It is benefit to stir
14
15
the FS with high viscosity and the stirring speed is controlled within 300 r/min. The results
16
17
18 can provide references for the FO pilot plant test on HSOB wastewater treatment.
19
20
21 The measured water flux could reach 29 L/m2∙h, which was 61% higher than the water
22
23
24 flux in the un-optimized operating conditions (18 L/m2∙h). Reverse salt flux was 1.17 mol/
25
26
27 m2∙h, and the salt rejection rate was 99% calculated by equation 4. This indicates that it is
28
29
important to optimize the operating conditions during the FO process.
30
31
32 The oil rejection rate of the membrane was evaluated (i.e., 3 M NaCl solution as the
33
34
35 DS, HSOB wastewater as the FS, cross-flow velocity of 15 cm/s, FO mode, 25 °C, running
36
37
38 for 120 min) by measuring the content of TOC and the results are shown in Figure 8.
39
40
41 700
42 (a) 559.8
The content of TOC (mg/L)
43 600
44 500
45 379.7
46 400
47 300
48
49 200
50 100
51
0
52
FS before treatment FS after treatment
53
54
55
56
57
58
59
25
60
1
2
3
4
5 12
6 (b)
9.894
10
7

8 8
9
10 6
11
12 4
13
2 1.527
14
15
0
16 DS before treatment DS after treatment
17
18
19
20 Figure 8. The TOC contents of the FS (a) and the DS (b) before and after treatment (3 M NaCl solution
21
22 as the DS, HSOB wastewater as the FS, cross-flow velocity of 15 cm/s, FO mode, 25 °C, running for
23
24
25 120 min).
26
27
28 Figure 8a shows that the TOC concentration of the FS increased after treatment
29
30
31 because the FS was more concentrated after the water penetrated to the DS. The TOC
32
33
34 concentration of the DS after treatment also increased in Figure 8b, because some oil
35
36 entered the DS through the membrane, which inevitably caused contamination to the
37
38
39 membrane. The rejection rate of oil was 96% calculated by equation 5, which showed that
40
41
42 the rejection effect of the FO membrane was good.
43
44
45 In order to determine the range of oil concentrations in HSOB wastewater treatment
46
47
48 available by the FO technology as well as to provide a reference for pretreatment, the
49
50 average water flux in 120 min was studied in different oil concentrations (from 100 mg/L
51
52
53 to 1300 mg/L) under the optimum experimental conditions and the result are presented in
54
55
56 Figure 9.
57
58
59
26
60
1
2
3
4
5 35
Different oil concentrations
6 30 30.08 Without oil
7 Water flux of 20 L/m2h

8 25 22.05 21.95 21.34
20.48 19.63
9 20 18.58
10 16.03
11 15
12 10
13
14 5
15 0
16 100 300 500 700 900 1100 1300
17 Oil concentration (mg/L)
18
19
20 Figure 9. Effect of different oil concentrations in the FS on the average water flux of the TFC FO
21
22 membranes (3 M NaCl solution as the DS, HSOB wastewater in 100 mg/L-1300 mg/L oil concentration
23
24
25 as the FS, cross-flow velocity of 15 cm/s, FO mode, 25 °C, running for120 min).
26
27
28 As shown in Figure 9, the water flux of the FS without oil was the largest while the
29
30
31 average water flux decreased with the increase of oil concentration in the FS, and the higher
32
33
34 the oil concentration, the faster the water flux decreased. The main reason for this
35
36 phenomenon was that high oil concentration increased the viscosity of the FS and boundary
37
38
39 layer resistance, which led to oil deposition on the membrane surface to cause membrane
40
41
42 organic fouling. This increased concentration polarization, blocked the membrane pores
43
44
45 and polluted the membrane.7,58 The water flux reduced greatly and FO will no longer
46
47
48 applicable to treat HSOB wastewater.
49
50 In addition, the water flux was more than 20 L/m2∙h when oil concentration was
51
52
53 between 100-700 mg/L. The oil concentration in oilfield produced wastewater before
54
55
56 entering a water treatment system is generally not more than 500 mg/L,59 so it is feasible
57
58
59
27
60
1
2
3
4 to treat oilfield produced wastewater with FO technology.
5
6
7 3.4 Membrane fouling and recovery
8
9
10 There are many salts and organics in HSOB wastewater, which can cause membrane
11
12
13 fouling during the treatment, so it was crucial to study the fouling and recovery properties
14
15
of the FO membrane. According to the different types of pollutants in membrane fouling,
16
17
18 the contaminants can be divided into organic substances, mineral salts, colloidal particles
19
20
21 and microbial species.60 The main influencing factors of membrane fouling are solution
22
23
24 compositions, membrane materials, hydraulic conditions and environmental conditions.61
25
26
27 However, organic fouling can be effectively controlled by optimizing the hydrodynamic
28
29
conditions of the FS without chemical cleaning agents in the FO process.16, 62 Generally,
30
31
32 backwashing is utilized to recover the properties of a polluted FO membrane.
33
34
35 Fouling and cleaning experiments were investigated with the FO system described
36
37
38 above (Figure 1). HSOB wastewater was treated for 3 h using 2 M NaCl DS at a cross-flow
39
40
41 velocity of 15 cm/s. Then the membrane was subjected to physical cleaning for 30min
42
43 using 5% of the recovered water (about 100 ml pure water) on both sides of the membrane
44
45
46 at a reverse cross-flow velocity of 24 cm/s. The results showed that the average water flux
47
48
49 of the FO membrane after cleaning achieved 99% compared with new membrane as shown
50
51
52 in Figure 10. This was attributed to the strong hydrophilic of the TFC FO membranes,
53
54
55 hydrophobic oil and natural osmotic pressure as a driving force in FO, which resulted to
56
57 contaminants accumulated on the membrane surface to form a loose and sparse fouling
58
59
28
60
1
2
3
4 layer. The fouling layer can be washed away by simple cross-flow cleaning.7,63,64
5
6
7
8 35
9 30 26.74 26.36
10 23.44

11 25
12 20
13
15
14
15 10
16
5
17
18 0
19 Before fouling After fouling After cleaning
20
21
22 Figure 10. The average water flux of the TFC FO membranes before fouling, after fouling and after
23
24
25 cleaning in FO mode (2 M NaCl solution as the DS, HSOB wastewater as the FS, backwashing velocity
26
27
28 of 24 cm/s, backwashing time of 30 min, FO mode, 25 °C).
29
30
31 4. CONCLUSIONS
32
33
34 This study focused on the feasibility and effectiveness analysis of HSOB wastewater
35
36 treatment by the FO membrane. Considering membrane materials, process characteristics
37
38
39 and properties of HSOB wastewater, the TFC polyamide FO membranes were fabricated.
40
41
42 Then the factors that influence the FO membrane properties on HSOB wastewater
43
44
45 treatment were evaluated and the optimized experimental conditions were determined.
46
47
48 Cross-flow velocity was 15 cm/s, and 3 M NaCl solution was chosen as the DS. The FO
49
50 mode was better to achieve a stable water flux. Temperature was 25 ℃, and the pressure
51
52
53 was atmospheric pressure.
54
55
56 The measured water flux could reach 29 L/m2∙h, which was 61% higher than the water
57
58
59
29
60
1
2
3
4 flux in the un-optimized operating conditions (18 L/m2∙h). The rejection rate of salt and oil
5
6
7 was 99% and 96%. When the oil concentration was between 100-700 mg/L, the separation
8
9
10 method of the FO membrane was utilized to treat HSOB wastewater with good effect. The
11
12
13 oil concentration in the oilfield produced wastewater is not more than 500 mg/L, so it is
14
15
feasible to treat the oilfield produced wastewater from polymer flooding with FO
16
17
18 technology.
19
20
21 AUTHOR INFORMATION
22
23
24 Corresponding Author
25
26 *
27 Tel.: +86-532-86983481. Fax: +86-532-86981815. E-mail: lpf@upc.edu.cn
28
29
ORCID
30
31
32 Pengfei Lin: 0000-0002-2403-6767
33
34
35 Notes
36
37
38 The authors declare no competing financial interest.
39
40
41 ACKNOWLEDGEMENTS
42
43 This study was supported by the Fundamental Research Funds for the Central
44
45
46 Universities (15CX02016A), the open project of State Key Joint Laboratory of
47
48
49 environmental simulation and pollution control (Tsinghua University) and the Science and
50
51
52 Technology Planning Project of Qingdao (15-9-2-111-nsh). Thanks to Dr. Edward C.
53
54
55 Mignot, Shandong University, for linguistic advice.
56
57
58
59
30
60
1
2
3
4 REFERENCES
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forward osmosis. Colloid Surf. A-Physicochem. Eng. Asp. 2016, 499, 163-172.
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22 Membr. Sci. 2010, 354 (1), 123-133.
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29 treatment. Acta Sci. Circum. 2016, 36 (8), 2701-2713 (in Chinese).
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membranes and study on its properties. M.S. Thesis, Harbin Institute of Technology, China, 2015 (in
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33 Chinese).
34 (45) Gray, G. T.; McCutcheon, J. R.; Elimelech, M. Internal concentration polarization in forward osmosis:
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36 role of membrane orientation. Desalination 2006, 197 (1-3), 1-8.
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during the nanofiltration of multi-ionic solutions: Influence of the filtrated solution and operating conditions.
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40 Water Res. 2013, 47 (7), 2260-2272.
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43 transport model to describe mixtures separation by nanofiltration: Model validation. AIChE J. 2011, 57 (4),
44 985 - 995.
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47 polarizations during forward osmosis processes. Desalination 2014, 338, 65-73.
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50 Environ. Sci. Technol. 2009, 43 (17), 6769-6775.
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57 and challenges. J. Membr. Sci. 2012, 396, 1-21.
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5 phenomenon: A comprehensive review. Desalination 2015, 374, 47-69.
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8 Effects of pH, calcium, membrane orientation, initial permeate flux and foulant composition. J. Environ. Sci.
9 2016, 46, 55-62.
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(54) Hawari, A. H.; Kamal, N.; Altaee, A. Combined influence of temperature and flow rate of feeds on the
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12 performance of forward osmosis. Desalination 2016, 398, 98-105.
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15 membrane orientation. Desalination 2013, 312, 88-98.
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for treating coal seam gas associated water: Flux and fouling behaviour. Desalination 2017, 403, 144-152.
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20 osmosis applications. J. Membr. Sci. 2011, 382, 308-315.
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23 membrane fouling during forward osmosis concentration of actual oily wastewater. J. Membr. Sci. 2017, 523,
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27 Jilin University, China, 2013 (in Chinese).
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29 (60) Arkhangelsky, E.; Wicaksana, F.; Chou, S.; Al-Rabiah, A. A.; Al-Zahrani, S. M.; Wang, R. Effects of
30 scaling and cleaning on the performance of forward osmosis hollow fiber membranes. J. Membr. Sci. 2012,
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415-416, 101-108.
32
33 (61) Liu, S.; Xie, C.; Zhou, N.; Wang, Y. Overview of research progress in membrane fouling and cleaning
34 for forward osmosis membrane. Water Purif. Technol. 2015, 34 (4), 23-30 (in Chinese).
35
36 (62) Mi, B.; Elimelech, M. Organic fouling of forward osmosis membranes: Fouling reversibility and
37 cleaning without chemical reagents. J. Membr. Sci. 2010, 348 (1-2), 337-345.
38
(63) Xue, N.; Pan, T. Research progress on characteization of concentration polarization and membrane
39
40 fouling of forward osmosis. Membr. Sci. Technol. 2015, 35 (5), 109-113 (in Chinese).
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42
43 osmosis distillation processes for treatment of fracturing flow-back. Petro. Ind. Appl. 2016, 35 (2), 5-10 (in
44 Chinese).
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Table of Content Graphic
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Tables
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7 Table 1. Water quality indicators (Unit: mg/L)
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9
10 Items Values
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13 K+, Na+ 1329.62
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16 Ca2+ 34.07
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18
Mg2+ 17.02
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21 Cl- 797.85
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24 SO42- 187.32
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27 HCO3- 1952.64
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30 CO32- 60.02
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Salinity 4378.54
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35 Suspended solids 15.80
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38 Oil 15.50
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42 Table 2. Properties of fabricated TFC FO membranes
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44
45 Water permeability A a NaCl permeability B b NaCl rejection Rb PH Thickness
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48 L/(m2hbar) L/(m2h) % μm
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50
51 TFC 1.26 0.17 98.4 2-11 92
52
53
a Measured
54 by RO using DI water as feed solution at pressure of 13.8 bar (200 psi).
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56 b Measured
57 by RO using 50 mM NaCl as feed solution at pressure of 13.8 bar (200 psi).
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Figures
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29 Figure 1. Flow chart of the FO membrane set-up.
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20 Figure 2. SEM images of the TFC FO membranes: (a) porous layer cross-sectional micrograph, (b)
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22 top view of dense surface layer.
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8 35
9 (a)
30
10

11 25
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13 20
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16 10
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5 DI water
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19 0
20 20 40 60 80 100 120
21 Time (min)
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25 1.4
26 1.2 (b) DI water
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28 1.0
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0.8
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31 0.6
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33 0.4
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0.2
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36 0.0
37 20 40 60 80 100 120
38 Time (min)
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41 Figure 3. The long-term water flux (a) and reverse salt flux (b) of the TFC FO membranes used for
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43 treating HSOB wastewater (2 M NaCl solution as the DS, DI water and HSOB wastewater as the FS,
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46 cross-flow rate of 15 cm/s, FO mode, 25 °C).
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7 1M NaCl
(a)
8 35 2M NaCl
9 30
3M NaCl

10 4M NaCl
11 25
12 20
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15
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15 10
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5
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18 0
20 40 60 80 100 120
19
20 Time (min)
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23 2.0
24 (b)
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26 1.5 1.26
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28 0.98
0.83
29 1.0
30 0.54
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32 0.5
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35 0.0
1 2 3 4
36
DS concentration (M)
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38
39 Figure 4. The water flux (a) and reverse salt flux (b) of the TFC FO membranes under different DS
40
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42 concentrations (1 M, 2 M, 3 M and 4 M NaCl solutions as the DS, HSOB wastewater as the FS, cross-
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45 flow rate of 15 cm/s, FO mode, 25 °C).
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1
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8 50
9 45 (a) 9cm/s
10 40 12cm/s

11 15cm/s
35 18cm/s
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30
13
25
14
15 20
16 15
17 10
18 5
19 0
20 20 40 60 80 100 120
21 Time (min)
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23
24
18
25
(b)
Reverse flux selectivity (L/mol)
26 16
13.26 12.98
27 14 12.3 12.73
28 12
29
10
30
31 8
32 6
33
4
34
35 2
36 0
37 9 12 15 18
38 Cross-flow velocity (cm/s)
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40
41 Figure 5. The water flux (a) and the reverse flux selectivity (b) of the TFC FO membranes at different
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43 cross-flow velocities of the DS and FS (2 M NaCl solution as the DS, HSOB wastewater as the FS,
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46 cross-flow rates of 9 cm/s, 12 cm/s, 15 cm/s, and 18 cm/s, FO mode, 25 °C).
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1
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6 30
7
0 r/min
8 100 r/min
25
9 300 r/min

10 500 r/min
11 20
12
13 15
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10
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18 5
20 40 60 80 100 120
19
20 Time (min)
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22 Figure 6. The water flux of the TFC FO membranes at different stirring rate on the FS side (2 M NaCl
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24
25 solution as the DS, HSOB wastewater as the FS, stirring rate of 0 r/min, 100 r/min, 300 r/min, and 500
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28 r/min, cross-flow rate of 15 cm/s, FO mode, 25 °C).
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8 35
9
10 30

11
12
25
13
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15 20
16
17 15 FO mode
18 PRO mode
19 10
20 20 40 60 80 100 120
21 Time (min)
22
23
24 Figure 7. The water flux of the TFC FO membranes under different membrane orientations (2 M NaCl
25
26
27 solution as the DS, HSOB wastewater as the FS, cross-flow rate of 15 cm/s, 25 °C).
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8 700
9 (a) 559.8

600
10
11 500
12 379.7
13 400
14
300
15
16 200
17
18 100
19 0
20 FS before treatment FS after treatment
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25 12
26 9.894
(b)
10
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8
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30 6
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32 4
33
34 2 1.527
35
36 0
37 DS before treatment DS after treatment
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40
41 Figure 8. The TOC contents of the FS (a) and the DS (b) before and after treatment (3 M NaCl solution
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43 as the DS, HSOB wastewater as the FS, cross-flow velocity of 15 cm/s, FO mode, 25 °C, running for
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46 120 min).
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8 35
9 Different oil concentrations
30 30.08 Without oil
10 Water flux of 20 L/m2h

11 25 22.05 21.95 21.34
12 20.48 19.63
20 18.58
13 16.03
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15
15
16 10
17
18 5
19 0
20 100 300 500 700 900 1100 1300
21 Oil concentration (mg/L)
22
23
24 Figure 9. Effect of different oil concentrations in the FS on the average water flux of the TFC FO
25
26
27 membranes (3 M NaCl solution as the DS, HSOB wastewater in 100 mg/L-1300 mg/L oil concentration
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29 as the FS, cross-flow velocity of 15 cm/s, FO mode, 25 °C, running for120 min).
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5 35
6
7 30 26.74 26.36
8 23.44

25
9
10 20
11
15
12
13 10
14
15 5
16
0
17 Before fouling After fouling After cleaning
18
19
20
21 Figure 10. The average water flux of the TFC FO membranes before fouling, after fouling and after
22
23
24 cleaning in FO mode (2 M NaCl solution as the DS, HSOB wastewater as the FS, backwashing velocity
25
26
27 of 24 cm/s, backwashing time of 30 min, FO mode, 25 °C).
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Water flux (L/m2h)

Water flux (L/m2h)

Water flux (L/m2h)

Water flux (L/m2h)

The content of TOC (mg/L)

Water flux (L/m2h)

Water flux (L/m2h)

Water flux (L/m2h)

Water flux (L/m2h)

Water flux (L/m2h)

Water flux (L/m2h)

Water flux (L/m2h)

The content of TOC (mg/L)

Water flux (L/m2h)

Water flux (L/m2h)

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