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Supercritical carbon dioxide (scCO2) is used in the food industry as a water-extracting drying agent. Once saturated with water, the scCO2 needs to be regenerated. A promising way of drying scCO2 is by using H2O permeable membranes. Ideally, these membranes demonstrate low CO2 permeability. Here, we investigated the CO2 permeability of three types of dense membranes, Nafion, Natural Rubber and PDMS, of which the latter in more detail because of its ease of handling. The experimental conditions, temperature and pressure, resulting in minimum CO2 permeability (=losses) were explored. Even though the absolute CO2 permeability depends on the intrinsic membrane material properties, its trend with increasing feed pressure is defined by the (supercritical) behavior of CO2, notably its density as a function of temperature and pressure. The data points to transitions within the supercritical regime, from the gaseous-like supercritical state to the liquid-like supercritical state, graphically visualized by the Widom line for CO2 density. Sorption measurements with PDMS membranes confirm this behavior that follows the diffusion-solution theory. In the gaseous state, the (normalized) permeability follows the (normalized) solubility, indicating a constant CO2 diffusivity. With increasing pressure and when entering the liquid-like (supercritical) regime, the diffusivity drops, resulting in a (normalized) permeability that starts to lag behind the (normalized) solubility.

Membrane technologies are nowadays widely used; especially various types of filtration or reverse osmosis in households, desalination plants, pharmaceutical applications etc. Facing water pollution, they are also applied to eliminate emerging contaminants from water. Incomplete knowledge directs the composition of membranes towards more and more dense materials known for their higher selectivity compared to porous constituents. This paper evaluates advantages and disadvantages of well-known membrane materials that separate on the basis of particle size, usually exposed to a large amount of water, versus dense hydrophobic membranes with target transport of emerging contaminants through a selective barrier. In addition, the authors present several membrane processes employing the second type of membrane.

O desenvolvimento de sistemas não-poluentes tem sido cada vez mais necessário para atender às exigências ambientais. Neste trabalho foram sintetizadas formulações de poliuretanos à base de água para a obtenção de membranas densas cujas propriedades mecânicas e de permeação a CO2 e N2 foram avaliadas. Foram empregados como monômeros polibutadieno líquido hidroxilado (HTPB), poli(glicol propilênico) (PPG), diisocianato de isoforona (IPDI) e ácido dimetilolpropiônico (DMPA). Os grupos carboxílicos foram neutralizados com trietilamina (TEA) e o extensor de cadeia utilizado foi a etilenodiamina (EDA). As membranas foram obtidas como filmes vazados a partir das dispersões aquosas. Os resultados mostraram que o aumento no teor de HTPB na formulação levou a uma maior resistência mecânica bem como a um aumento na permeabilidade e na seletividade das membranas a CO2. The performance of dense membranes based on nonpolluting systems of polyurethane aqueous dispersions was evaluated. The mechanical properties and the selectivity and permeability to CO2 and N2 were determined. The aqueous systems were based on hydroxyl-terminated polybutadiene (HTPB), poly(propylene glycol) (PPG), isophorone diisocyanate (IPDI), and dimethylolpropionic acid (DMPA). The membranes obtained from cast films provided higher permeability and selectivity to CO2 as the HTPB content increased. The tensile strength and the modulus values of the materials increased and the elongation decreased with higher amounts of HTPB. As a result, the presence of HTPB improved the mechanical resistance, the permeability and the selectivity to CO2 of the polyurethane membranes.