ABSTRACT
The uptake and adsorption enthalpy of carbon dioxide at 0.2 bar have been studied in three different topical porous MOF samples, HKUST-1, UiO-66(Zr), and MIL-100(Fe), after having been pre-equilibrated under different relative humidities (3, 10, 20, 40%) of water vapor. If in the case of microporous UiO-66, CO(2) uptake remained similar whatever the relative humidity, and correlations were difficult for microporous HKUST-1 due to its relative instability toward water vapor. In the case of MIL-100(Fe), a remarkable 5-fold increase in CO(2) uptake was observed with increasing RH, up to 105 mg g(-1) CO(2) at 40% RH, in parallel with a large decrease in enthalpy measured. Cycling measurements show slight differences for the initial three cycles and complete reversibility with further cycles. These results suggest an enhanced solubility of CO(2) in the water-filled mesopores of MIL-100(Fe).
ABSTRACT
This work reports the adsorption and coadsorption data of CO(2)/CH(4)/CO mixtures on several metal-organic frameworks [MOFs; MIL-100(Cr), MIL-47(V), MIL-140(Zr)-A, Cu-btc, and MIL-53(Cr)] and compares them with reference adsorbents, that is, zeolite NaX and an activated carbon material, AC35. We also evaluate the effect of H(2)O on CO(2) adsorption and on the stability of the structures. Based on the experimental adsorption data, the performance potential of MOFs in several pressure swing adsorption processes is estimated by making a ranking of working capacities and separation factors. We discuss the separation of biogas, the purification of H(2) produced by steam reforming of methane, and the removal of CO(2) from synthesis gas in IGCC (integrated gasification combined cycle) systems. Some MOFs are very well placed in the ranking of (isothermal) working capacity vs. selectivity. Yet, performance is not the only criterion for the selection of MOFs. Ease and cost of synthesis and long-term stability are other important aspects that have to be taken into account.
Subject(s)
Carbon Dioxide/chemistry , Organometallic Compounds/chemistry , Pressure , Adsorption , Carbon Dioxide/isolation & purification , Carbon Monoxide/chemistry , Carbon Monoxide/isolation & purification , Hot Temperature , Methane/chemistry , Methane/isolation & purification , Water/chemistry , Zeolites/chemistryABSTRACT
In addition to its high thermal stability, repetitive hydration/dehydration tests have revealed that the porous zirconium terephthalate UiO-66 switches reversibly between its dehydroxylated and hydroxylated versions. The structure of its dehydroxylated form has thus been elucidated by coupling molecular simulations and X-ray powder diffraction data. Infrared measurements have shown that relatively weak acid sites are available while microcalorimetry combined with Monte Carlo simulations emphasize moderate interactions between the UiO-66 surface and a wide range of guest molecules including CH(4), CO, and CO(2). These properties, in conjunction with its significant adsorption capacity, make UiO-66 of interest for its further evaluation for CO(2) recovery in industrial applications. This global approach suggests a strategy for the evaluation of metal-organic frameworks for gas-based applications.
