Complex treatment of oily polluted waters by modified melamine foams: from colloidal emulsions to a free oil removal

Abstract

This study deals with the efficient, low-cost, and scalable treatment of oily polluted waters including colloidal emulsions, oil-in-water mixtures, and free oil removal using melamine foams (MFs) modified by ferric chloride (FeCl₃). Modified foams have superhydrophobic character due to the coordination of Fe³⁺ with free electron pairs on nitrogen and oxygen atoms within the melamine structure. The water contact angles (WCA) were 146° ± 2°, 148° ± 4°, 153° ± 2°, and 150° ± 4° for foams modified by the solutions with concentrations of 0.001 M, 0.005 M, 0.01 M, and 0.02 M, respectively. This modification enables the efficient treatment of various oil/water systems, including oil/water colloidal emulsions (99 vol% of the droplets have dimensions below 500 nm), oil-in-water mixtures up to 40 weight % of the oil component, and "free" oil removal as it was demonstrated in this study for the first time. The emulsions containing 100 ppm diesel oil (DO) were separated with 91.4% efficiency, and the mixtures containing 20 and 40 weight % DO were separated with 99.9% efficiency. Modified foams also quickly remove free DO from the water surface, absorbing 95 g/g DO, whereas water sorption was negligible. The separation of colloidal oil in water emulsions represents the key finding of this study as it indicates the applicability of the treated MFs for the treatment of emulsified industrial wastewater. The demulsification mechanism is based on multiple diffusion processes running at different time scales, including diffusion of the emulsion into the foam and diffusion of oil droplets within the foam, combined with parallel adsorption of oil droplets onto the solid skeleton of the foam. A multiplied usage of these foams for all these niche operations was also proven. The application of our current study with previous studies on modified MFs and polyurethane for water oil separation utilization is summarized in Table S1 ESI.

Keywords: Absorption capacity; Emulsions; Melamine foams; Oil removal; Superhydrophobicity; Superoleophilicity.