Green Synthesis of Cellulose Acetate Mixed Matrix Membranes: Structure–Function Characterization

Although membrane technology is widely used in different gas separation applications, membrane manufacturers need to reduce the environmental impact during the membrane fabrication process within the framework of the circular economy by replacing toxic solvents, oil-based polymers, and such by more sustainable alternatives. These include environmentally friendly materials, such as biopolymers, green solvents, and surfactant free porous fillers. This work promotes the use of environmentally sustainable and low toxic alternatives, introducing the novel application of cellulose acetate (CA) as a biopolymer in combination with dimethyl carbonate (DMC) as a greener solvent and different inorganic fillers (Zeolite-A, ETS-10, AM-4 and ZIF-8) prepared without the use of toxic solvents or reactants. Hansen Solubility Parameters were used to confirm the polymer–solvent affinity. Pure CA and mixed matrix membranes were characterized regarding their hydrophilicity by water uptake and contact angle measurements, thermal stability by TGA, mechanical resistance, ATR-FTIR and scanning electron microscopy before evaluating the gas separation performance by single gas permeability of N₂, CH₄, and CO₂. Conditioning of the CA membranes is observed causing reduction of the CO₂ permeability values from 12,600 Barrer for the fresh 0.5 wt % ETS-10/CA membrane to 740 Barrer for the 0.5 wt % ZIF-8/CA membranes, corresponding to 24% and 4.2% reductions in CO₂/CH₄ selectivity and 30% and 24% increase in CO₂/N₂ selectivity for the same membranes. The structure–relationship was evaluated by phenomenological models which are useful at low filler loading considering flux direction and particle shape and size but still fail to explain the interactions between the DMC green solvent and CA matrix and fillers that are influencing gas transport performance different than other CA membranes.