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

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.

The Separation of Oil/Water Mixtures by Modified Melamine and Polyurethane Foams: A Review.

Melamine (MA) and polyurethane (PU) foams, including both commercial sponges for daily use as well as newly synthesized foams are known for their high sorption ability of both polar and unipolar liquids. From this reason, commercial sponges are widely used for cleaning as they absorb a large amount of water, oil as well as their mixtures. These sponges do not preferentially absorb any of those components due to their balanced wettability. On the other hand, chemical and physical modifications of outer surfaces or in the bulk of the foams can significantly change their original wettability. These treatments ensure a suitable wettability of foams needed for an efficient water/oil or oil/water separation. MA and PU foams, dependently on the treatment, can be designed for both types of separations. The particular focus of this review is dealt with the separation of oil contaminants dispersed in water of various composition, however, an opposite case, namely a separation of water content from continuous oily phase is also discussed in some extent. In the former case, water is dominant, continuous phase and oil is dispersed within it at various concentrations, dependently on the source of polluted water. For example, waste waters associated with a crude oil, gas, shale gas extraction and oil refineries consist of oily impurities in the range from tens to thousands ppm [mg/L]. The efficient materials for preferential oil sorption should display significantly high hydrophobicity and oleophilicity and vice versa. This review is dealt with the various modifications of MA and PU foams for separating both oil in water and water in oil mixtures by identifying the chemical composition, porosity, morphology, and crosslinking parameters of the materials. Different functionalization strategies and modifications including the surface grafting with various functional species or by adding various nanomaterials in manipulating the surface properties and wettability are thoroughly reviewed. Despite the laboratory tests proved a multiply reuse of the foams, industrial applications are limited due to fouling problems, longer cleaning protocols and mechanical damages during performance cycles. Various strategies were proposed to resolve those bottlenecks, and they are also reviewed in this study.