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<p>Emulsion wastewater contains insoluble oils and polycyclic aromatic hydrocarbons (PAHs), which poses significant environmental and health risks. Membrane separation technology, known for its simplicity, efficiency, energy-saving and environmental friendliness, has demonstrated substantial potential for treating emulsion wastewater. In this study, the ionic liquid (IL), 1-vinyl-3-butylimidazolium tetrafluoroborate ([VBIM][BF₄]), was grafted onto the polyvinylidene fluoride (PVDF) membrane surface via electron beam-induced polymerization. Subsequently, a straightforward anion exchange process introduced sulfonated butyl-β-cyclodextrin (SBE-β-CD⁻) into the membranes, resulting in PVDF-g-IL-SBE-β-CD membranes. The modified PVDF membranes exhibited exceptional oil rejection efficiencies (achieving 94.3–99.5%) and remarkable antifouling properties in emulsion wastewater treatment. These enhancements are primarily attributed to the integration of hydrophilic ionic liquids into the membrane matrix, which significantly improves surface hydrophilicity and flux recovery rate, thereby enhancing overall membrane performance. Furthermore, the modified PVDF membranes exhibited excellent removal performance for low molecular weight PAHs in emulsions, owing to π–π interactions between the imidazolium groups and PAHs, as well as the host–guest inclusion effect of the cyclodextrin cavities. The membrane achieved a naphthalene (NAP) removal efficiency of up to 98.9%, with a water flux of 750.9&#xa0;L&#xa0;m⁻<sup>2&#xa0;</sup>h⁻<sup>1</sup> and an emulsion flux of 296.2&#xa0;L&#xa0;m⁻<sup>2</sup>&#xa0;h⁻<sup>1</sup>. The best-performing M15-SBE-β-CD membrane demonstrated emulsion fluxes exceeding 200&#xa0;L&#xa0;m⁻<sup>2</sup>&#xa0;h⁻<sup>1</sup> and achieved over 95% removal efficiency of other typical PAHs, including phenanthrene (PHE) and anthracene (ANT). This study offers valuable insights and optimization strategies for advancing membrane technology in the efficient treatment of emulsion wastewater, pioneering the simultaneous filtration of emulsions and PAHs in a single step.</p> Graphical abstract <p></p>

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Enhanced oil-in-water emulsion separation using polyvinylidene fluoride (PVDF) membranes modified via electron beam IL grafting and cyclodextrin anion exchange

  • 期刊论文

  • 发表日期：

    2025年7月25日

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  • Yong Xu,
  • Jiahui Shi,
  • Xiuhong Wu,
  • Zeni Zheng,
  • Li Chen,
  • Jincan Yan,
  • Sheng Han

摘要

Emulsion wastewater contains insoluble oils and polycyclic aromatic hydrocarbons (PAHs), which poses significant environmental and health risks. Membrane separation technology, known for its simplicity, efficiency, energy-saving and environmental friendliness, has demonstrated substantial potential for treating emulsion wastewater. In this study, the ionic liquid (IL), 1-vinyl-3-butylimidazolium tetrafluoroborate ([VBIM][BF₄]), was grafted onto the polyvinylidene fluoride (PVDF) membrane surface via electron beam-induced polymerization. Subsequently, a straightforward anion exchange process introduced sulfonated butyl-β-cyclodextrin (SBE-β-CD⁻) into the membranes, resulting in PVDF-g-IL-SBE-β-CD membranes. The modified PVDF membranes exhibited exceptional oil rejection efficiencies (achieving 94.3–99.5%) and remarkable antifouling properties in emulsion wastewater treatment. These enhancements are primarily attributed to the integration of hydrophilic ionic liquids into the membrane matrix, which significantly improves surface hydrophilicity and flux recovery rate, thereby enhancing overall membrane performance. Furthermore, the modified PVDF membranes exhibited excellent removal performance for low molecular weight PAHs in emulsions, owing to π–π interactions between the imidazolium groups and PAHs, as well as the host–guest inclusion effect of the cyclodextrin cavities. The membrane achieved a naphthalene (NAP) removal efficiency of up to 98.9%, with a water flux of 750.9 L m⁻2 h⁻1 and an emulsion flux of 296.2 L m⁻2 h⁻1. The best-performing M15-SBE-β-CD membrane demonstrated emulsion fluxes exceeding 200 L m⁻2 h⁻1 and achieved over 95% removal efficiency of other typical PAHs, including phenanthrene (PHE) and anthracene (ANT). This study offers valuable insights and optimization strategies for advancing membrane technology in the efficient treatment of emulsion wastewater, pioneering the simultaneous filtration of emulsions and PAHs in a single step.

Graphical abstract