Oily sludge is a complex emulsified waste consisting of water, oil, and solid particles. Conventional treatments are often inefficient, energy-intensive, and prone to causing secondary pollution. This study proposes a green demulsification technology based on ozone micro–nanobubbles (O
3MNBs) by constructing an
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Oily sludge is a complex emulsified waste consisting of water, oil, and solid particles. Conventional treatments are often inefficient, energy-intensive, and prone to causing secondary pollution. This study proposes a green demulsification technology based on ozone micro–nanobubbles (O
3MNBs) by constructing an experimental system to analyze its effects and mechanisms of action on oily sludge treatment. The O
3MNBs exhibited a mean particle size of 831 nm and generated a substantial amount of hydroxyl radicals (·OH, 250.4 μmol·L
−1) in situ. Compared with conventional aeration, the dissolved ozone concentration and residence time in water of O
3MNBs increased by 192% and 213%, respectively. During bubble collapse, intense pressure waves and high-speed microjets were generated to disrupt sludge aggregates, promoting the dispersion of sludge particles while simultaneously stripping oil films. Thus, the oil removal rate reached 41.5%, demonstrating the high demulsification efficiency of O
3MNBs. Furthermore, ozone and ·OH attacked alkane C-H bonds in the oil phase, oxidizing hydrophobic films into hydrophilic products and decomposing surfactants that stabilize emulsions. This process promoted oil droplet coalescence and degradation into small organic molecules. After O
3MNB treatment, the absorption peak of alkane C-H bonds gradually reduced, while a new C=O absorption peak appeared. This study provides a theoretical foundation and technical support for environmentally sustainable treatment of oily sludge by O
3MNB application, offering an effective alternative to chemical demulsification without secondary pollution.
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