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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2018, Vol. 12 Issue (2) : 262-272    https://doi.org/10.1007/s11705-017-1682-7
RESEARCH ARTICLE
Metal cation removal by P(VC-r-AA) copolymer ultrafiltration membranes
Nachuan Wang1, Jun Wang1, Peng Zhang2, Wenbin Wang1, Chuangchao Sun1, Ling Xiao2, Chen Chen2, Bin Zhao2, Qingran Kong1, Baoku Zhu1()
1. Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
2. Hainan Litree Purifying Technology Co., Ltd., Haikou 571126, China
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Abstract

A series of amphiphilic copolymers containing poly(vinyl chloride-r-acrylic acid) (P(VC-r-AA) ) was synthesized and used to prepare membranes via a non-solvent induced phase separation method. The prepared membranes were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and water contact angle and zeta potential measurements. The copolymer P(VC-r-AA) chains did not dissolved in a coagulation bath, indicating that the AA segments were completely retained within the membrane. Enriching degree of AA segments in surface layer was 2 for copolymer membrane. In addition, the introduction of AA segments made the membrane electronegative and hydrophilic so that the membrane was sensitive to the solution pH. The fouling resistance, adsorption of Cu(II), Cr(III) and Ce(IV) ions and the desorption properties of the membranes were also determined. The copolymer membranes exhibited good antifouling performance with a fouling reversibility of 92%. The membranes also had good adsorption capacities for Cu(II), Cr(III) and Ce(IV) ions. The optimal pH for Cu(II) adsorption was 6 and the copolymer membrane has potential applications for low concentration Cu(II) removal.
Keywords poly(vinyl chloride-r-acrylic acid)      negatively charged PVC membrane      anti-fouling      heavy metal adsorption      Cu(II) removal     
Corresponding Author(s): Baoku Zhu   
Just Accepted Date: 17 August 2017   Issue Date: 09 May 2018
 Cite this article:   
Nachuan Wang,Jun Wang,Peng Zhang, et al. Metal cation removal by P(VC-r-AA) copolymer ultrafiltration membranes[J]. Front. Chem. Sci. Eng., 2018, 12(2): 262-272.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1682-7
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I2/262
Raw materials Units LA3 LA6 LA10 LA30
Deionized water G 2000 2000 2000 2000
Initiator G 30 30 30 30
Emulsifier G 3 3 3 3
VC G 970 940 900 700
AA G 30 60 100 300
Tab.1  Raw materials used to synthesize copolymers
Polymer Mna) PDI AA /wt-%b) Membrane ID
PVC 7.1 × 104 1.91 0 M0
LA3 7.3 × 104 1.87 2.64 M1
LA6 6.9 × 104 1.86 4.92 M2
LA10 6.5 × 104 1.83 8.99 M3
LA30 6.2 × 104 1.96 27.21 M4
Tab.2  The molecular weight, PDI, composition and ID of polymer membranes
Fig.1  SEM images of membranes cast from pristine PVC (M0) and copolymers (M1-4)
Fig.2  XPS spectra of PVC membrane (M0) and copolymer membrane surfaces (M1-4)
Membrane C /% O /% Cl /% AA segments wt-% in membrane AA segments wt-% in surface layer a) Enrichment ratio b)
M0 66.76 0 33.24 ? ? ?
M1 66.20 2.83 30.97 2.64 5.02 1.90
M2 65.82 5.22 28.96 4.92 9.48 1.92
M3 64.95 10.07 24.97 8.99 18.75 2.08
M4 63.02 24.37 12.61 27.21 53.51 1.96
Tab.3  The chemical compositions in surface layer of PVC and copolymer membranes
Fig.3  Time-dependent contact angles for the PVC (M0) and copolymer (M1-4) membrane surfaces. LA3 (M1), LA6 (M2), LA10 (M3) and LA30 (M4)
Fig.4  Zeta potentials as a function of pH for the PVC (M0) and copolymer (M1-4) membrane surfaces. LA3 (M1), LA6 (M2), LA10 (M3) and LA30 (M4)
Fig.5  (a) Solute separation curves plotted on a log-normal probability scale and (b) pore radius distribution curves for copolymer membranes
Membrane Mean pore size µp/nm Geometric std. dev. σp
M1 3.30 1.80
M2 4.02 1.81
M3 4.53 1.82
M4 5.31 1.86
Tab.4  Geometric mean pore sizes and standard deviations for copolymer membranes calculated from separation curves
Fig.6  BSA fouling performance of the pristine PVC (M0) and copolymer M3 and M4 membranes: time dependent flux for 3 stages: (a) pure water filtration, (b) 1000 ppm BSA PBS filtration, and (c) pure water filtration after back flushing at 0.01 MPa for 30 min
fouling properties Membrane
M0 M3 M4
pH 2.4 4.8 7.4 11 2.4 4.8 7.4 11 2.4 4.8 7.4 11
FRR 0.74 0.65 0.81 0.86 0.62 0.41 0.92 0.96 0.56 0.38 0.99 0.99
Rt 0.28 0.42 0.21 0.17 0.42 0.60 0.13 0.11 0.44 0.62 0.08 0.09
Rr 0.02 0.07 0.03 0.03 0.04 0.01 0.05 0.08 0.00 0.00 0.08 0.08
Rir 0.26 0.35 0.19 0.14 0.38 0.59 0.08 0.04 0.44 0.62 0.01 0.01
RRF 0.06 0.17 0.13 0.20 0.10 0.02 0.36 0.69 0.01 0.01 0.89 0.92
RIF 0.94 0.83 0.87 0.80 0.90 0.98 0.64 0.31 0.99 0.99 0.11 0.08
Tab.5  Flux recovery and filtration resistance of different membranes
Fig.7  Charge state of BSA and carboxyl groups and their dominant interactions at different pH values
Fig.8  Ion adsorption for the pure PVC membrane (M0) and for the copolymer membranes M1, M2, M3 and M4 (pH= 6.0)
Fig.9  (a) The Cu(II) adsorption capacity of the P(VC-r-AA) M4 membrane at different pH values and (b) desorption (washed at pH 2)/re-adsorption (at pH 6) cycles
Fig.10  Adsorption kinetics of Cu(II) ions at pH 6 and desorption kinetics of Cu(II) ions at pH 2 on M4
Fig.11  Cu(II) removal during filtration cycles using M3 and M4 at pH 6 and at pH 2 (feed solution: 10 mg/L Cu II, 100 kPa, 25 °C). Regeneration was conducted by washing with acidic water (pH 2)
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