Shaping of MIL-53-Al and MIL-101 MOF for CO2/CH4, CO2/N2 and CH4/N2 separation

Metal-organic frameworks (MOF) are promising materials for gas storage and separation. The formulation and shaping of MOFs in mechanically stable bead forms is an essential requirement for their practical application as an adsorbent for gas and liquid mixture separations. In this work, MIL-53-Al and MIL-101 MOF beads are synthesized using sodium alginate as a binder, and calcium chloride as a gelling agent. The synthesized MIL-53-Al and MIL-101 MOF beads are characterized by powder X-ray diffraction (PXRD), BET surface area, porosity analysis from N2 uptake data at 77 K, FTIR, TGA, and scanning electron microscopy (SEM). The isothermal equilibrium adsorption uptake of CH4 and N2 gases is measured up to 10 bar pressure while the CO2 equilibrium uptake is measured up to 1 bar at 298 and 313 K respectively. The isotherm data of all adsorbates are fitted in Dual Site Langmuir (DSL) isotherm equations. The adsorption selectivity for CH4/N2, CO2/CH4, and CO2/N2 binary systems are predicted using the Ideal Adsorbed Solution Theory (IAST) method. The dynamic column breakthrough experiments are carried out on MIL-53-Al beads for CH4/N2 (30:70 and 50:50 v/v), CO2/CH4 (45:55 v/v) and CO2/N2 (15: 85 v/v) feed mixtures. The IAST selectivity and breakthrough time obtained under the same superficial velocity, pressure, and temperature conditions follow the order CO2/N2 > CO2 /CH4 > CH4/N2. The MIL-53-Al beads show higher CH4/N2, CO2/CH4, and CO2/N2 selectivity for the targeted mixtures than MIL-101 beads.