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Frontiers of Chemical Science and Engineering
ISSN 2095-0179   
ISSN 2095-0187(Online)   
CN 11-5981/TQ   
2015 Impact Factor: 1.043

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Front. Chem. Sci. Eng.    2016, Vol. 10 Issue (4) : 562-574     DOI: 10.1007/s11705-016-1588-9
RESEARCH ARTICLE |
Thin-film composite forward osmosis membranes with substrate layer composed of polysulfone blended with PEG or polysulfone grafted PEG methyl ether methacrylate
Baicang Liu1,2(),Chen Chen3,Pingju Zhao1,2,Tong Li4,Caihong Liu5,Qingyuan Wang1,2,Yongsheng Chen6,John Crittenden6
1. College of Architecture and Environment, Sichuan University, Chengdu 610065, China
2. Institute of New Energy and Low Carbon Technology, Sichuan University, Chengdu 610207, China
3. Litree Purifying Technology Co., Ltd, Haikou 571126, China
4. Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
5. State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
6. School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA
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Abstract  

To advance commercial application of forward osmosis (FO), we investigated the effects of two additives on the performance of polysulfone (PSf) based FO membranes: one is poly(ethylene glycol) (PEG), and another is PSf grafted with PEG methyl ether methacrylate (PSf-g-PEGMA). PSf blended with PEG or PSf-g-PEGMA was used to form a substrate layer, and then polyamide was formed on a support layer by interfacial polymerization. In this study, NaCl (1 mol?L−1) and deionized water were used as the draw solution and the feed solution, respectively. With the increase of PEG content from 0 to 15 wt-%, FO water flux declined by 23.4% to 59.3% compared to a PSf TFC FO membrane. With the increase of PSf-g-PEGMA from 0 to 15 wt-%, the membrane flux showed almost no change at first and then declined by about 52.0% and 50.4%. The PSf with 5 wt-% PSf-g-PEGMA FO membrane showed a higher pure water flux of 8.74 L?m−2?h−1 than the commercial HTI membranes (6–8 L?m−2?h−1) under the FO mode. Our study suggests that hydrophobic interface is very important for the formation of polyamide, and a small amount of PSf-g-PEGMA can maintain a good condition for the formation of polyamide and reduce internal concentration polarization.

Keywords thin-film composite      forward osmosis      amphiphilic copolymer      interfacial polymerization      poly(ethylene glycol)     
Corresponding Authors: Baicang Liu   
Just Accepted Date: 26 August 2016   Online First Date: 13 September 2016    Issue Date: 29 November 2016
URL:  
http://academic.hep.com.cn/fcse/EN/10.1007/s11705-016-1588-9     OR     http://academic.hep.com.cn/fcse/EN/Y2016/V10/I4/562
No. TFC FO membrane NMP /g PSf /g Additives Additive/PSf /(%, wt·wt−1 )
PEG /g PSf-g-PEGMA /g
M1 PSf 88 12 0 0 0
M2 PSf with 5 wt-% PEG 87.4 12 0.6 0 5
M3 PSf with 10 wt-% PEG 86.8 12 1.2 0 10
M4 PSf with 15 wt-% PEG 86.2 12 1.8 0 15
M5 PSf with 5 wt-% PSf-g-PEGMA 87.4 12 0 0.6 5
M6 PSf with 10 wt-% PSf-g-PEGMA 86.8 12 0 1.2 10
M7 PSf with 15 wt-% PSf-g-PEGMA 86.2 12 0 1.8 15
Tab.1  Compositions of support layer membrane casting solutions
Fig.1  Schematic diagram of FO system
Fig.2  SEM images of the surface (left column) and cross-section (right column) of seven substrate membranes. (a,b) M1; (c,d) M2; (e,f) M3; (g,h) M4 (i,j) M5; (k,l) M6; (m,n) M7
No. TFC FO membrane with additive Intrinsic permeability, A /(L?m−2?h−1?bar−1) NaCl permeability, B /(L?m−2?h−1) Structural parameter, S /µm Support layer thicknesses /µm
M1 PSf 1.03±0.17 5.62±0.92 278 153.47±15.32
M2 PSf with 5 wt-% PEG 0.36±0.08 2.17±0.47 782 152.13±17.89
M3 PSf with 10 wt-% PEG 0.39±0.16 0.43±0.18 814 161.65±8.88
M4 PSf with 15 wt-% PEG 0.25±0.10 0.80±0.33 1193 174.31±19.17
M5 PSf with 5 wt-% PSf-g-PEGMA 0.93±0.25 5.82±1.58 299 153.82±12.51
M6 PSf with 10 wt-% PSf-g-PEGMA 0.35±0.01 3.00±0.06 3086 153.35±18.92
M7 PSf with 15 wt-% PSf-g-PEGMA 0.41±0.05 0.94±0.12 757 146.07±25.47
Tab.2  FO Membrane properties
No. TFC FO membrane with additive Daverage/nm Dmax/nm Pore density /m−2 Surface porosity /%
M1 PSf 9.0±1.6 43.8 1.6 × 1014 1.38
M2 PSf with 5 wt-% PEG 8.9±1.5 36.8 1.4 × 1014 1.29
M3 PSf with 10 wt-% PEG 7.6±1.8 24.3 6.7 × 1013 0.37
M4 PSf with 15 wt-% PEG 7.9±1.4 28.8 1.1 × 1014 0.72
M5 PSf with 5 wt-% PSf-g-PEGMA 7.8±1.7 28.8 1.5 × 1014 0.97
M6 PSf with 10 wt-% PSf-g-PEGMA 7.5±1.5 24.9 1.7 × 1014 0.95
M7 PSf with 15 wt-% PSf-g-PEGMA 7.9±1.6 27.9 1.3 × 1014 0.99
Tab.3  Summary of pore size distribution statistics
Fig.3  The variation of contact angle with time for (a) different amounts (0, 5, 10 and 15 wt-%) of PEG additives and (b) different amounts (5, 10 and 15 wt-%) of PSf-g-PEGMA additives
Fig.4  SEM images of the surface of FO membranes. (a) M1, (b) M2, (c) M3, (d) M4, (e) M5, (f) M6, and (g) M7
Fig.5  Comparison of FO water fluxes of different membranes: commercial HTI, PSf with different amounts of PEG and PSf-g-PEGMA,12 wt-% PSf with 0 wt-% DMF, 12 wt-% PSf 12 wt-% with PET not wetted [22], and 0 wt-% sulphonated polymer [25]. Experimental conditions for FO water flux measurements were as follows: 1.0 mol?L?1 NaCl as draw solution, DI water as feed solution, and 25 °C
Fig.6  Comparison of RO (a) water flux variation, and (b) salt rejection due to substrate layer with different amounts of PEG and PSf-g-PEGMA added in the casting solution. Experimental conditions for RO flux were as follows: 400 psi (27.6 bar) applied pressure, and 50 mmol?L−1 NaCl as feed solution, 25 °C. Note: PSf with 10 wt-% PSf-g-PEGMA was tested under 200 psi due to its low strength
Fig.7  Conceptual illustration of different scenarios: (a) PSf, (b) PSf with PEG, (c) PSf with 5 wt-% PSf-g-PEGMA, and (d) PSf with 10 or 15 wt-% PSf-g-PEGMA
A Intrinsic water permeability coefficient, L?m?2?h?1?bar?1
B NaCl permeability coefficient, L?m?2?h?1
Cb bulk feed salt concentration, mmol?L?1
Cp permeate salt concentration, mmol?L?1
D salt diffusion coefficient, m2?s?1
Jw pure water flux, L?m?2?h?1
K resistance to diffusion, s?m?1
DP pressure difference, bar
R salt rejection, %
S membrane structural parameter, µm
ts membrane thickness, µm
t membrane tortuosity
ε membrane porosity
πD,bbulk osmotic pressure of the draw solution, bar
πF,mosmotic pressure at the membrane surface on the feed side, bar
Dp bulk osmotic pressure difference, bar
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