GO/Al2O3复合纳滤膜的制备及其稳定性能研究

doi:10.11949/0438-1157.20200205

摘要/Abstract

摘要：

以平均孔径为20 nm的Al₂O₃管式超滤膜为载体，经多巴胺改性后，利用压力驱动沉积法成功制备出能在水溶液中长期稳定的GO/Al₂O₃复合纳滤膜，并通过改变负载量实现了对GO层厚的调控。结果表明，随错流时间的延长，不同GO负载量下GO/Al₂O₃复合纳滤膜的纯水渗透系数均呈现先降低后稳定的趋势。且随着GO负载量的增加，稳态纯水渗透系数逐渐降低；当GO负载量增加到90 mg/m²后，GO/Al₂O₃复合纳滤膜对一二价盐的渗透系数与截留率均无显著变化。同时，由于盐测试过程中残余的盐离子在GO片层间产生了交联作用，从而导致随着在纯水中存放时间的延长，不同GO负载量的GO/Al₂O₃复合纳滤膜对一二价盐的截留率均呈上升趋势。GO负载量为140 mg/m²的GO/Al₂O₃复合纳滤膜在水中浸泡680 h后对1 mmol/L Na₂SO₄的截留率可达到91.0%。GO/Al₂O₃复合纳滤膜对四种一二价盐的截留率满足：R(Na₂SO₄) > R(MgSO₄) > R(NaCl) > R(MgCl₂)。

关键词: 氧化石墨烯, Al₂O₃管式膜, 多巴胺, 负载量, 纳滤, 稳定性

Abstract:

Using an tubular Al₂O₃ ultrafiltration membrane with an average pore diameter of 20 nm as the carrier, after modified by dopamine, a pressure-driven deposition method was used to successfully prepare a GO/Al₂O₃ composite nanofiltration membrane that can be stable in aqueous solution for a long time. The thickness of GO layer can be controlled by changing the loading amount. The results showed that the pure water permeability of all GO/Al₂O₃ composite nanofiltration membranes decreased and then reached a steady state during the cross-flow filtration. In addition, the pure water permeability of GO/Al₂O₃ composite nanofiltration membranes decreased as the GO loading amount increased. The permeability and rejection of GO/Al₂O₃ composite nanofiltration membranes remained stable when GO loading amount was greater than 90 mg/m². As the storage time (in pure water) extended, the cross-linking of GO sheets caused by residual salt ions during tests led to a higher rejection of GO/Al₂O₃ composite nanofiltration membranes towards monovalent and divalent salts. After being immersed in pure water for 680 h, the GO/Al₂O₃ composite nanofiltration membrane with GO loading amount of 140 mg/m² showed the highest Na₂SO₄ rejection of 91.0%. The rejections of GO/Al₂O₃ composite nanofiltration membranes towards four salt solutions were as follows: R(Na₂SO₄) > R(MgSO₄) > R(NaCl) > R(MgCl₂).

Key words: graphene oxide, tubular Al₂O₃ membranes, dopamine, loading amount, nanofiltration, stability

中图分类号:

TQ 028.8

汪菊, 牛淑锋, 费莹, 漆虹. GO/Al₂O₃复合纳滤膜的制备及其稳定性能研究[J]. 化工学报, 2020, 71(6): 2795-2803.

Ju WANG, Shufeng NIU, Ying FEI, Hong QI. Fabrication and stability of GO/Al₂O₃ composite nanofiltration membranes[J]. CIESC Journal, 2020, 71(6): 2795-2803.

图/表 10

图1 GO/Al2O3复合纳滤膜的制备流程示意图

Fig.1 Schematic diagram of fabrication process of GO/Al2O3 composite nanofiltration membranes

图2 管式膜错流过滤装置示意图

Fig.2 Schematic diagram of cross-flow filtration apparatus for tubular membranes

图4 Al2O3膜与PDA-Al2O3膜的纯水通量

Fig.4 Pure water flux of Al2O3 membrane and PDA-Al2O3 membrane

图3 Al2O3膜与PDA-Al2O3膜的SEM图(图(a)、(c)中内插图为相应膜表面的光学照片)

Fig.3 SEM images of Al2O3 membrane and PDA-Al2O3 membrane(The insets of (a) and (c) is the optical images of the corresponding membrane surface)

图5 不同GO负载量下GO/Al2O3复合纳滤膜的SEM照片[表面(a)~(d),断面(c)~(h)与水接触角(i)~(l)]

Fig.5 SEM images[surface(a)—(d),cross-section(c)—(h) and water contact angles(i)—(l)] of GO/Al2O3 composite nanofiltration membranes with different GO loading amounts

图6 GO/Al2O3复合纳滤膜的纯水渗透系数

Fig.6 Pure water permeability of GO/Al2O3 composite nanofiltration membranes

图7 GO/Al2O3复合纳滤膜对四种单组分盐溶液的截留性能

Fig.7 Rejection of GO/Al2O3 composite nanofiltration membranes towards four salt solutions

图8 GO/Al2O3复合纳滤膜对盐溶液的截留性能随浸泡时间延长的变化

Fig.8 Variation of rejection of GO/Al2O3 composite nanofiltration membranes (immersed in deionized water for different time) towards salt solutions

表1 GO/Al2O3复合纳滤膜的性能及稳定性对比

Table 1 Comparison of properties including stability of GO/Al2O3 composite nanofiltration membranes

膜	分离体系	性能	稳定时间
GO/Al₂O₃ (片式)^[19]	水溶液中去除苯酚 (盲端过滤)	对1 mmol/L苯酚水溶液的渗透率为1.153 L/(m²·h·bar)，截留率为67.8%	16 h
SG@GO/Al₂O₃ (管式)^[1]	脱除水中的染料分子(EBT)(错流过滤)	对0.2 mmol/L EBT的渗透率为33 L/(m²·h·bar)，截留率为98%	48 h
GO/PDA-Al₂O₃ (片式)^[18]	海水渗透汽化	75℃下对含盐量3.5%（质量）的海水的渗透率为32.1 kg/(m²·h)，脱盐率为99.7%	336 h
GO/Al₂O₃ (管式)(本文)	单组分盐溶液截留 (错流过滤)	对1 mmol/L Na₂SO₄的渗透率为0.2 L/(m²·h·bar)，截留率为91.0%	680 h

图9 GO/Al2O3复合纳滤膜的纳米划痕图

Fig.9 Nano-scratch of GO/Al2O3 composite nanofiltration membranes

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GO/Al₂O₃复合纳滤膜的制备及其稳定性能研究

Fabrication and stability of GO/Al₂O₃ composite nanofiltration membranes

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