Development of Amine-Functionalized Metal-Organic Frameworks Hollow Fiber Mixed Matrix Membranes for CO2 and CH4 Separation: A Review.

CO2 separation from raw natural gas can be achieved through the use of the promising membrane-based technology. Polymeric membranes are a known method for separating CO2 but suffer from trade-offs between its permeability and selectivity. Therefore, through the use of mixed matrix membranes (MMMs) which utilizes inorganic or hybrid fillers such as metal-organic frameworks (MOFs) in polymeric matrix, the permeability and selectivity trade-off can be overcome and possibly surpass the Robeson Upper Bounds. In this study, various types of MOFs are explored in terms of its structure and properties such as thermal and chemical stability. Next, the use of amine and non-amine functionalized MOFs in MMMs development are compared in order to investigate the effects of amine functionalization on the membrane gas separation performance for flat sheet and hollow fiber configurations as reported in the literature. Moreover, the gas transport properties and various challenges faced by hollow fiber mixed matrix membranes (HFMMMs) are discussed. In addition, the utilization of amine functionalization MOF for mitigating the challenges faced is included. Finally, the future directions of amine-functionalized MOF HFMMMs are discussed for the fields of CO2 separation.

Cellulose acetate-based membranes by interfacial engineering and integration of ZIF-62 glass nanoparticles for CO2 separation.

Composite membranes typically used for gas separation are susceptible to interfacial voids and CO2 plasticization which adversely affects the gas permeation performance. This paper evaluates routes towards the enhancement of CO2 permeation performance and CO2 plasticization resistance of composite membranes using non-stoichiometric ZIF-62 MOF glass and cellulose acetate (CA). Single and mixed gas permeation results, obtained with CO2 and CH4, demonstrate that the presence of ZIF-62 glass in CA polymer enhanced the CO2 permeability and CO2/CH4 ideal selectivity from 15.8 to 84.8 Barrer and 12.2-35.3, respectively. The composite membrane loaded with 8 wt% of ZIF-62 glass showed the highest CO2 permeability and CO2/CH4 ideal selectivity of 84.8 Barrer and 35.3, which were 436.7% and 189.3% higher compared to the pristine CA membrane, respectively. A CO2 plasticization pressure of 26 bar was achieved for the composite membranes, which is 160% higher compared to the pristine CA membranes, at about 10 bar. The mechanisms for the materials stabilization and greater separation performance were attributed to higher pore size (7.3 Å) and significant CO2 adsorption on the unsaturated metal nodes followed by metal cites electrostatic interaction with CO2. These findings confirm the potential of ZIF-62 glass materials as promising materials solutions towards the design of composite membranes for CO2 separation at industrial scale.