This study introduces an innovative approach to designing membranes capable of separating CO₂ from industrial gas streams at higher temperatures. The novel membrane design seeks to leverage a well-researched, high-temperature CO₂ adsorbent, hydrotalcite, by transforming it into a membrane. This was achieved by combining it with an amorphous organo-silica-based matrix, extending the polymer-based mixed-matrix membrane concept to inorganic compounds. Following the membrane material preparation and investigation of the individual membrane in Part 1 of this study, we examine its permeation and selectivity here. The pure 200 nm thick hydrotalcite membrane exhibits Knudsen behavior due to large intercrystalline pores. In contrast, the organo-silica membrane demonstrates an ideal selectivity of 13.5 and permeance for CO₂ of 1.3 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 25 °C, and at 150 °C, the selectivity is reduced to 4.3. Combining both components results in a hybrid microstructure, featuring selective surface diffusion in the microporous regions and unselective Knudsen diffusion in the mesoporous regions. Further attempts to bridge both components to form a purely microporous microstructure are outlined.

This study introduces an innovative approach to designing membranes capable of separating CO2 from industrial gas streams at higher temperatures. The novel membrane design seeks to leverage the well-researched high-temperature CO2 adsorbent, hydrotalcite, by transforming it into a membrane. This is achieved by combining it with an amorphous organo-silica-based matrix, extending the polymer-based Mixed Matrix Membrane concept to inorganic compounds. Following the membrane material preparation and investigation of the individual membrane in Part 1 of this study, we examine its permeation and selectivity here. The pure 200 nm thick hydrotalcite membrane exhibits Knudsen behavior due to large intercrystalline pores. In contrast, the organo-silica membrane demonstrates a permselectivity of 13.5 and permeance for CO2 of 1.3 107 mol m2 s1 Pa1 at 25°C, at 150°C the good separation behavior is reduced. Combining both components results in a hybrid microstructure, featuring selective surface diffusion in the microporous regions and unselective Knudsen diffusion in the mesoporous regions. Further attempts to bridge both components to form a purely microporous microstructure are outlined.

For industrial CO₂ utilization, the supply of concentrated CO₂ within a continuous, high-volume stream at high temperatures remains a substantial requirement. Membrane processes offer a simple and efficient method to provide CO₂ in this form. While several organo-silica-based membranes have been developed for CO₂/N₂ separation under these conditions, there is no standardized framework guiding comparability and optimization. Therefore, we present these membranes in a Robeson-like plot across various temperatures. Utilizing a standard 1,2-bis(triethoxysilyl)-ethane (BTESE) precursor and a simplified sol–gel method, we prepared a microporous membrane layer and characterized it for an exemplary comparison. This characterization includes key parameters for mixed-gas applications: (1) temperature-dependent single- and mixed-gas permeances to observe interactions, (2) the impact of the driving forces in mixtures (vacuum and concentration) to distinguish between permselectivity and the separation factor clearly, and (3) influence of the support structure to enable permeability calculations at elevated temperatures. Furthermore, a quick interpretation method for assessing the membrane’s microstructure is presented. A qualitative microstructure assessment can be achieved by analyzing the temperature dependencies of the three major diffusion mechanisms that simultaneously occur—Knudsen, surface, and activated diffusion.