Preparation and enduring effect oil-water separation performance of water-based superhydrophilic anti-fouling composite mesh membrane
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摘要: 石油化工和机械制造等领域普遍存在含油污水，直接排放不仅浪费水、油资源，污染生态环境，还影响人类与其他生物的生存与健康。传统的油水分离方法局限性强、经济性差、分离效率不高。以316不锈钢丝网为基底，研发了耐长期水泡与耐油污染的超亲水水下疏油网膜，通过优选水性丙烯酸与水性环氧清漆共混树脂作为粘结剂，对基底采用植酸预处理，采用一步喷涂法制备出了纯水性涂层涂覆的超亲水水下疏油网膜。对不同含油污水的分离效率均能够达到98%以上，水通量能够达到14000 L/(m2·h·bar) 以上，耐油压为4.65 kPa。循环分离正己烷污水50次后，网膜的分离效率仍然能够达到98%以上。耐水泡180天后仍保持超亲水性及6500 L/(m2·h·bar)以上的水通量。添加微量表面活性剂十二烷基硫酸钠后，经过50次污染-清洗循环后网膜的水通量衰减＜50%。这一研究为精细化含油污水处理领域超亲水分离网膜的研发与制备提供了一定借鉴与技术参考。Abstract: Oily sewage is ubiquitous in the petrochemical industry, machinery manufacturing and other fields. Direct discharge not only wastes water and oil resources, pollutes the ecological environment, but also affects the survival and health of human beings and other organisms. The traditional oil-water separation method has strong limitations, such as poor economy and low separation efficiency. Based on 316 stainless mesh, a superhydrophilic/underwater oleophobic membrane that was resistant to long-term water immersion and oil pollution was developed. The water-based acrylic acid resin and water-based epoxy topcoat resin were selected as the binder, and the substrate was pretreated with phytic acid. The superhydrophilic/underwater oleophobic membrane coated with water-based coating was prepared using a one-step spraying method. It is found that the separation efficiency of wastewater with different oils can reach more than 98%, the water flux can reach more than 14000 L/(m2·h·bar), and the intrusion pressure of oil is 4.65 kPa. After 50 cycles of separating wastewater with N-hexane, the separation efficiency of the membrane can still reach more than 98%. After 180 days of water immersion, the membrane still maintains superhydrophilicity with a water flux of more than 6500 L/(m2·h·bar). After adding a small amount of surfactant of sodium dodecyl sulfate, the water flux of the membrane decreases by less than 50% after 50 pollution and cleaning cycles. This study provides technical references for the development and preparation of superhydrophilic separation membranes in the field of refined oily wastewater treatment.
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图 1 超亲水网膜的制备示意图
Figure 1. Schematic diagram of preparation of the superhydrophilic mesh membrane
CNC—Cellulose nanocrystals; PA—Phytic acid
图 2 环氧地坪漆(EP-D)与环氧清漆(EP-T)改性网膜泡水期涂层变化
Figure 2. Change of mesh membranes modified by the water-based epoxy floor (EP-D) and epoxy topcoat (EP-T) duration the water immersion
图 3 (a) 水性丙烯酸树脂在不同预处理不锈钢丝网上的附着力；(b) 经不同预处理的丝网在空气中静置24 h后的光学照片
Figure 3. (a) Adhesion force of water-based acrylic acid resin on different pretreated stainless steel meshes; (b) Optical photos of different pretreated meshes after leaving in the air for 24 h
图 4 超亲水网膜的润湿性：(a) 水接触角(WCA)及水下CCl4接触角(UWOCA)；(b) 空气中水滴铺展时间
Figure 4. Wettability of the superhydrophilic mesh membrane: (a) Water contact angle (WCA) and underwater oil contact angle (UWOCA) of CCl4; (b) Spreading time of water droplet in air
图 5 原始不锈钢丝网 (a) 和超亲水网膜 (b) 的SEM图像
Figure 5. SEM images of the original stainless steel mesh (a) and the superhydrophilic mesh membrane (b)
图 6 (a) 植酸预处理制备的超亲水网膜用于分离正己烷/水混合物；(b) 油水分离原理示意图
Figure 6. (a) N-hexane/water mixture separated by the superhydrophilic mesh membrane pretreated by phytic acid; (b) Schematic diagram of oil-water separation principle
Δp—Intrusion pressure; θα—Advancing contact angle; R—Radius of the meniscus
图 7 (a) 超亲水网膜对不同含油污水的分离效率；(b) 循环分离正己烷污水50次超亲水网膜的分离效率；(c) 超亲水网膜的分离水通量
Figure 7. (a) Oil-water separation efficiency of the superhydrophilic mesh membrane for wastewater with different oils; (b) Oil-water separation efficiency of superhydrophilic mesh membrane for wastewater with N-hexane after 50 separation cycles; (c) Water flux of superhydrophilic mesh membrane during the separation
图 8 超亲水网膜泡水180天期间：(a) 水滴铺展时间；(b) 水通量变化
Figure 8. Superhydrophilic mesh membrane immersed into water for 180 days: (a) Change in spreading time; (b) Change in water flux
图 9 超亲水网膜泡水180天内微观形貌的变化：(a) 泡水前；(b) 泡水50天；(c) 泡水80天；(d) 泡水120天；(e) 泡水150天；(f) 泡水180天
Figure 9. Change in microscopic morphologies of superhydrophilic mesh membrane after immersing into water for 180 days: (a) Original; (b) 50 days; (c) 80 days; (d) 120 days; (e) 150 days; (f) 180 days
图 10 超亲水网膜润湿性的变化：(a) 不同pH环境浸泡24 h；(b) 在pH=2、pH=12的溶液中浸泡7天；超亲水网膜在不同pH溶液中浸泡7天后的表面形貌SEM图像：(c) pH=2；(d) pH=12
Figure 10. Change in wettability of superhydrophilic mesh membrane: (a) Immersing in different pH solutions for 24 h; (b) Immersing in solutions of pH=2 and pH=12 for 7 days; SEM images of superhydrophilic mesh membrane after immersing in different pH solutions for 7 days: (c) pH=2; (d) pH=12
图 11 (a) 原始不锈钢丝网无法脱附油污；(b) 超亲水网膜可有效脱附油污；(c) 干燥状态下粘附在超亲水网膜上的大豆油在水下快速自行脱附
Figure 11. (a) Original stainless steel mesh cannot desorb the oil; (b) Superhydrophilic mesh membrane can effectively desorb the oil; (c) Rapid self-desorption of the soybean oil adhered to the dry superhydrophilic mesh membrane underwater
图 12 (a) 添加少量十二烷基硫酸钠(SDS)后制得的超亲水网膜涂层SEM图像；(b) 超亲水网膜及其加入SDS后分别经过原油污染-清洗50次循环后水通量衰减情况；(c) 100 g砝码压力下粒径为25.4 μm的砂纸摩擦100次后超亲水网膜的润湿性变化
Figure 12. (a) SEM images of the superhydrophilic mesh membrane prepared by adding a small amount of sodium dodecyl sulfate (SDS); (b) Water flux attenuation of the superhydrophilic mesh membrane and after adding SDS suffering from 50 cycles of crude oil pollution and cleaning respectively; (c) Wettability change of superhydrophilic mesh membrane after 100 abrasion tests with 100 g weight and sandpaper with a particle size of 25.4 μm
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