Water Vapor Adsorption Capacity Loss of Molecular Sieves 4A, 5A, and 13X Resulting from Methanol and Heptane Exposure.

Zeolite-based molecular sieves are applied in industrial dehydration units for their high water uptake capacities and extremely low equilibrium pressure of water vapor. During their operational life, they tend to lose their water vapor adsorption capacity slowly. To optimize the usage of molecular sieves in dryer units, it is vital to understand the mechanism(s) leading to deactivation. In this work, the capacity loss was studied by exposing LTA- and FAU-type zeolites to methanol and heptane vapors under relatively harsh conditions using repetitive adsorption/regeneration cycles. A simple microflow unit was designed and used for the deactivation experiments. The water vapor adsorption capacity of the resulting samples was measured using a gravimetric analyzer. In addition, they were characterized by classic XRD, 13C NMR, and TGA techniques. The crystallinity of fresh and spent zeolite XRD patterns was not drastically affected even after exposure to the contaminants. It was found that methanol easily gave rise to a severe loss of water vapor adsorption capacity, much more so than heptane. Water vapor uptake in the methanol exposed samples is ∼50% lower than that for the fresh zeolites. This is attributed to nonvolatile, residual hydrocarbons.

Morphology, Activation, and Metal Substitution Effects of AlPO4-5 for CO2 Pressure Swing Adsorption.

Aluminophosphate, AlPO4-5, an AFI zeotype framework consisting of one-dimensional parallel micropores, and metal-substituted AlPO4-5 were prepared and studied for CO2 adsorption. Preparation of AlPO4-5 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 CO2 adsorption performance. Among the various metal-substituted analogs, FeAPO-5 was found to exhibit the highest CO2 capacity at all pressures tested (up to 4 bar). Among the Fe-substituted samples, xFeAPO-5, with x being the Fe/Al2O3 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 CO2 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. CO2 adsorption kinetics was found to follow a pseudo-first-order model. The robust nature of AlPO4-5-based adsorbents, their unique one-dimensional pore configuration, fast kinetics, and low heat of adsorption make them promising for pressure swing adsorption of CO2 at industrial scale.

Metal Organic Framework - Based Mixed Matrix Membranes for Carbon Dioxide Separation: Recent Advances and Future Directions.

Gas separation and purification using polymeric membranes is a promising technology that constitutes an energy-efficient and eco-friendly process for large scale integration. However, pristine polymeric membranes typically suffer from the trade-off between permeability and selectivity represented by the Robeson's upper bound. Mixed matrix membranes (MMMs) synthesized by the addition of porous nano-fillers into polymer matrices, can enable a simultaneous increase in selectivity and permeability. Among the various porous fillers, metal-organic frameworks (MOFs) are recognized in recent days as a promising filler material for the fabrication of MMMs. In this article, we review representative examples of MMMs prepared by dispersion of MOFs into polymer matrices or by deposition on the surface of polymeric membranes. Addition of MOFs into other continuous phases, such as ionic liquids, are also included. CO2 separation from hydrocarbons, H2, N2, and the like is emphasized. Hybrid fillers based on composites of MOFs with other nanomaterials, e.g., of MOF/GO, MOF/CNTs, and functionalized MOFs, are also presented and discussed. Synergetic effects and the result of interactions between filler/matrix and filler/filler are reviewed, and the impact of filler and matrix types and compositions, filler loading, surface area, porosity, pore sizes, and surface functionalities on tuning permeability are discoursed. Finally, selectivity, thermal, chemical, and mechanical stability of the resulting MMMs are analyzed. The review concludes with a perspective of up-scaling of such systems for CO2 separation, including an overview of the most promising MMM systems.