超亲水水下超疏油复合不锈钢网的制备及在油水分离中的应用

doi:10.16085/j.issn.1000-6613.2024-1123

摘要/Abstract

摘要：

采用聚多巴胺（PDA）涂覆策略，将聚乙烯醇（PVA）与戊二醛（GA）反应后形成的交联网格结构与凹凸棒石（APT）、二氧化钛纳米颗粒（TiO₂）共混后，黏附在不锈钢网表面。成功制备了超亲水/水下超疏油PTAS复合网膜。通过优选反应条件，对不锈钢网的表面润湿性进行了优化。采用FTIR、XRD、SEM表征了网膜表面的官能团、化学结构及微观形貌，评价了其润湿性、化学稳定性、油水分离性能、重复利用性及抗油污性能。结果显示：当聚多巴胺溶液浸泡时间为12h，聚乙烯醇浓度为0.03g/mL，凹凸棒石粉加量为0.02g/mL，二氧化钛纳米颗粒加量为0.01g/mL时，PTAS网在空气中水相接触角为0°，水下正己烷、二氯甲烷、汽油、煤油、柴油的接触角均大于154°，具有优秀的热稳定性及化学稳定性，对5种油水混合物的分离效率均高于99%，通量最高可达21156L/(m²·h)。经过20次循环实验后，分离效率仍高于97.2%，通量衰减小于10%，表现出优秀的重复利用性。从化学反应与物理受力的角度，结合改进的Young’s、Cassie方程和Young-Laplace方程，分析了PTAS复合不锈钢网的抗油污性能、润湿改性和油水分离的机理。

关键词: 特殊润湿性, 油水分离, 膜, 毛细管力, 重复利用性

Abstract:

A polydopamine (PDA) coating strategy was used to adhere the cross-linked lattice structure formed by the reaction of poly(vinyl alcohol) with glutaraldehyde on the surface of a stainless steel mesh after mixing with augite and titanium dioxide to adhere nanoparticles. The superhydrophilic/underwater superoleophobic PTAS mesh was successfully fabricated. The surface wettability of the stainless steel mesh was optimized by preferred reaction conditions. The functional groups, chemical structure and microscopic morphology of the mesh film surface were characterized by FTIR, XRD and SEM, and their wettability, chemical stability, oil-water separation performance, reusability and oil resistance were evaluated. The results showed that when the polydopamine solution was soaked for 12 hours, the concentration of polyvinyl alcohol was 0.03g/mL, the addition of eggplant powder was 0.02g/mL and the addition of titanium dioxide nanoparticles was 0.01g/mL, the WCA of the PTAS mesh was 0°, and the UWOCAs of n-hexane, methylene chloride, gasoline, kerosene and diesel were more than 154°, which had excellent separation efficiency of the five oil-water mixtures with higher than 99% and the flux was up to 21156L/(m²·h). After 20 experimental cycles, the separation efficiency was still over 97.2% and the flux attenuation was less than 10%, showing excellent reusability. The mechanisms of oil resistance, wetting modification and oil-water separation of the PTAS mesh were analyzed from the perspective of chemical reaction and physical force, combined with the improved Young's, Cassie equations and the Young-Laplace equation.

Key words: special wettability, oil-water separation, membranes, capillary force, reusability

中图分类号:

TE99

付沅峰, 范振忠, 臧鑫, 仝其雷, 刘金刚. 超亲水水下超疏油复合不锈钢网的制备及在油水分离中的应用[J]. 化工进展, 2025, 44(6): 3659-3670.

FU Yuanfeng, FAN Zhenzhong, ZANG Xin, TONG Qilei, LIU Jingang. Preparation of superhydrophilic underwater superoleophobic composite SSM and its application in oil-water separation[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3659-3670.

图/表 16

图1 超亲水水下超疏油PTAS网的制备过程

图2 油水分离装置1—铁架台；2—带刻度的上管柱；3—复合不锈钢网；4—油水分离器；5—下管柱；6—烧杯

图3 多巴胺在碱性环境中的氧化自聚合机理

图4 聚乙烯醇与戊二醛交联反应

图5 反应条件与不锈钢网表面润湿性的关系

图6 PTAS复合不锈钢网的FTIR图谱

图7 PTAS复合不锈钢网的XRD图谱

图8 PTAS复合不锈钢网制备过程中不同阶段的SEM图像

图9 未处理不锈钢网及PTAS网的润湿性分析

图10 PTAS复合不锈钢网的稳定性分析

图11 PTAS复合不锈钢网分离正己烷/水的过程

图12 PTAS复合不锈钢网对油水混合物的分离效率和通量

图13 超亲水水下超疏油PTAS网表面的复合涂层

表1 原始不锈钢网表面水下油滴接触角的理论值与测量值

油样	γ_o/mN·m^-1	γ_w/mN·m^-1	γ_ow/mN·m^-1	θ_o/(°)	θ_w/(°)	θ_ow/(°)	$θ o w'$ /(°)
正己烷	18.1	72	51.1	42.7	73.0	98.7	104.4
二氯甲烷	21.1	72	28.1	37.5	73.7	102.4	103.9
汽油	22.0	72	26.2	44.2	72.5	103.2	105.1
煤油	28.2	72	29.6	56.5	73.4	99.8	102.4
柴油	26.8	72	19.6	1.0	72.8	99.2	101.6

表1 原始不锈钢网表面水下油滴接触角的理论值与测量值

油样	γ_o/mN·m^-1	γ_w/mN·m^-1	γ_ow/mN·m^-1	θ_o/(°)	θ_w/(°)	θ_ow/(°)	$θ o w'$ /(°)
正己烷	18.1	72	51.1	42.7	73.0	98.7	104.4
二氯甲烷	21.1	72	28.1	37.5	73.7	102.4	103.9
汽油	22.0	72	26.2	44.2	72.5	103.2	105.1
煤油	28.2	72	29.6	56.5	73.4	99.8	102.4
柴油	26.8	72	19.6	1.0	72.8	99.2	101.6

图14 PTAS复合不锈钢网的毛细管力模型

表2 水下不同油相侵入PTAS复合不锈钢网的渗透压力

油样	γ_ow/mN·m^-1	θ_ow/(°)	∆p_c^w/Pa
正己烷	51.1	155.4	6.2×10⁴
二氯甲烷	28.1	154.5	3.4×10⁴
汽油	26.2	155.0	3.2×10⁴
煤油	29.6	154.8	3.6×10⁴
柴油	19.6	154.6	2.4×10⁴

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