目的 制备一种无氟超疏水/超亲油珍珠岩粉末材料,以实现油水混合物的高效分离,并可实现水包油乳化液的油水分离,为海洋溢油处理、工业含油废水净化等场景提供绿色高效的油水分离方案。方法 通过化学改性法对天然珍珠岩颗粒进行表面能改性,经研磨、硬脂酸-乙醇溶液修饰、高温烘干、二次研磨等工艺,制备出具有超疏水/超亲油性的珍珠岩粉末。系统表征了改性后材料的润湿性、微观结构和元素组成。进一步将超疏水/超亲油珍珠岩粉末置于无纺布过滤包中,通过吸附法油水分离和过滤法油水分离进行油水混合物的分离;采用强力搅拌破乳的方式实现水包油乳化液的油水分离。结果 改性珍珠岩粉末表现出优异的超疏水性与超亲油性,水在表面的接触角大于150°,且不含氟元素。该材料可高效分离多种油水混合物,对多种油水混合物的吸附/过滤分离效率均超过92%,并可在较为恶劣的条件（如强力搅拌、紫外照射、高温、酸碱盐溶液等环境）下实现油水分离,展现出较好的稳定性、耐用性和重复利用性。此外,对表面活性剂稳定的水包油乳化液仍可实现油水分离。结论 成功制备出超疏水/超亲油珍珠岩粉末,可实现复杂油水混合物及乳化液的高效分离,分离效率高且具有较高的分离纯度。该油水分离方法无需外加试剂或复杂设备,环境友好、成本低廉,在海上溢油应急处理、工业含油废水净化等领域具有广阔的应用前景。
Abstract
This study is dedicated to the development of a novel fluorine-free superhydrophobic and superoleophilic perlite powder designed for the high-efficiency separation of oil/water mixtures, including challenging oil-in-water emulsions. Its primary objective is to provide a green, cost-effective, and robust solution for critical environmental remediation scenarios such as marine oil spill recovery and the purification of industrial oily wastewater. The fabrication methodology involves a meticulous chemical modification process of natural perlite particles. This process commences with coarse grinding of the raw perlite, followed by a critical surface energy modification step using a stearic acid solution in ethanol. The treated powder is then subject to a controlled high-temperature drying process to ensure stable bonding of the hydrophobic agents, culminating in a final micronization step through secondary grinding to achieve a fine, functionalized powder. This synthesis strategy successfully constructs a hierarchical micro/nanostructure and grafts low-surface-energy groups onto the perlite, contributing to the achievement of the desired wettability. A comprehensive suite of characterization techniques, including scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), are employed to analyze the surface morphology and elemental composition. Wettability assessments confirm the excellent performance of the modified perlite powder, demonstrating a superhydrophobic state with a water contact angle exceeding 150° and a superoleophilic state with an oil contact angle close to 0°. Crucially, EDS analysis verifies the complete absence of fluorinated compounds, underscoring the environmentally friendly nature of the modification process. For practical application, the superhydrophobic perlite powder is packaged into non-woven fabric filters. Its separation performance is rigorously evaluated through two primary mechanisms: adsorption-driven oil/water separation and filtration-driven oil/water separation. The results are highly promising, showing separation efficiencies consistently above 92% for a diverse range of oil/water mixtures (heavy oil: dichloromethane, light oil: peanut oil, diesel, n-hexane). In addition, the separated water is extracted using carbon tetrachloride and the oil content in the water is tested by FTIR spectroscopy. It can be observed that the oil content in the water after separation from the four different oil/water mixtures is relatively low, indicating that the water obtained by this separation method has high purity. In addition, the separation efficiency is still larger than 90% after 20 times filiation oil/water separation, indicating good stability and reusability. Furthermore, the superhydrophobic/superoleophilic perlite powder exhibits remarkable stability and durability in harsh environmental tests. It maintains high separation efficiency after prolonged exposure to intense mechanical stirring, UV radiation (365 nm, 6 W), elevated temperature (up to 90 ℃), and highly corrosive acidic (pH=1), alkaline (pH=11), and sodium chloride aqueous solution (3.5wt.%). The results confirm its potential for use in real-world applications. A significant achievement of this study is the superhydrophobic/superoleophilic perlite powder's ability to effectively separate oil-in-water emulsions. By leveraging a vigorous stirring process that induces demulsification, the superhydrophobic powder successfully coalesces and captures the dispersed oil droplets. In conclusion, this research successfully fabricates a fluorine-free, superhydrophobic/superoleophilic perlite powder via a simple and scalable chemical modification method. The material exhibits outstanding efficiency, exceptional stability, and superior durability in separating both oil/water mixtures and oil-in-water emulsions. The developed material holds substantial promise for broad applications in emergency marine oil spill response and the treatment of industrial effluents, offering a practical pathway for mitigating water pollution.
关键词
超疏水表面 /
微/纳结构 /
低表面能 /
油水分离 /
水包油乳化液
Key words
superhydrophobic surface /
micro/nanostructure /
low surface energy /
oil/water separation /
oil-in-water emulsion
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基金
山东省自然科学基金（ZR2025QC1172,ZR2024QE379）
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