Morphology, Activation, and Metal Substitution Effects of AlPO(4)-5 for CO(2) Pressure Swing Adsorption

Aluminophosphate, AlPO(4)-5, an AFI zeotype framework consisting of one-dimensional parallel micropores, and metal-substituted AlPO(4)-5 were prepared and studied for CO(2) adsorption. Preparation of AlPO(4)-5 by using different activation methods (calcination and pyrolysis), incorporation of different metals/ions (Fe, Mg, Co, and Si) into the framework using various concentrations, and manipulation of the reaction mixture dilution rate and resulting crystal morphology were examined in relation to the CO(2) adsorption performance. Among the various metal-substituted analogs, FeAPO-5 was found to exhibit the highest CO(2) capacity at all pressures tested (up to 4 bar). Among the Fe-substituted samples, xFeAPO-5, with x being the Fe/Al(2)O(3) molar ratio in the synthesis mixture (range of 2.5:100–10:100), 5FeAPO-5 exhibited the highest capacity (1.8 mmol/g at 4 bar, 25°C) with an isosteric heat of adsorption of 23 kJ/mol for 0.08–0.36 mmol/g of CO(2) loading. This sample also contained the minimum portion of extra-framework or clustered iron and the highest mesoporosity. Low water content in the synthesis gel led to the formation of spherical agglomerates of small 2D-like crystallites that exhibited higher adsorption capacity compared to columnar-like crystals produced by employing more dilute mixtures. CO(2) adsorption kinetics was found to follow a pseudo–first-order model. The robust nature of AlPO(4)-5–based adsorbents, their unique one-dimensional pore configuration, fast kinetics, and low heat of adsorption make them promising for pressure swing adsorption of CO(2) at industrial scale.