Determination of the location of coke in catalysts by a novel NMR-based, liquid-porosimetry approach.
In this work, a new technique, suitable for chemically-heterogeneous materials, has been used to characterise the structural properties of porous heterogeneous catalysts. A liquid-liquid exchange (LLE) process within nanoporous catalysts has been followed using NMR relaxometry and NMR diffusometry. In order to validate the new technique, two model materials were used. First, a chemically-pure, sol-gel silica, with a simple, mono-disperse pore-space, was studied. The second model material was a bidisperse, eggshell Pt-alumina catalyst. The Pt-alumina catalyst was studied both fresh, and coked following chemical reaction. The degree of structural and chemical complexity added by coking was restricted by the localisation of the coke deposition to the Pt-eggshell layer. Under so-called 'metered' supply conditions, when a high affinity liquid (water) displaced a low affinity liquid (cyclohexane) from the sol-gel silica, entrapment of the low affinity liquid was observed which was similar to that observed in mercury porosimetry. In a similar experiment, comparing LLE in fresh and coked samples of the Pt-alumina catalyst pellets, it was found, for the fresh sample, that water initially displaced cyclohexane from a sub-set of the most accessible, smallest pores, as might expected under metered conditions, but this did not occur for coked catalysts. This finding suggested coking had removed some smaller pores located close to the surface of the pellet, in agreement with where the Pt-metal was preferentially located and coking was known to have occurred.
Solvent-dependent permeability in asymmetric ceramic membranes with tortuous or non-tortuous mesopores
Abstract Solvent-dependent transport and the role of surface interactions were examined in commercial mesoporous ceramic membranes using permeability and thermoporometry measurements. The membranes chosen were titania (TiO 2 ) with tortuous interconnected pores (1, 5, and 50 kDa, corresponding to pore diameters of ca. 8.2, 18.3, and 33.2 nm, respectively) and alumina (Al 2 O 3 ) with non-tortuous 20 nm cylindrical pores. A pre-water/solvent/post-water permeability cycle was employed to account for structural differences between membranes and to gauge the effect of residual solvent on water permeability at different temperatures. Our results suggest that in both types of membranes, restricted permeability of 1-butanol and cyclohexane was due to a combination of surface sorption and an increase in disjoining pressure due to solvation forces. Sorption and solvation forces were prevalent as their length scales were on the same order of magnitude as the pore radii. For 1-butanol, chemisorption changed the surfaces from hydrophilic to hydrophobic, and led to a significant decrease in post-water permeability. While Darcy's law could not describe 1-butanol and cyclohexane permeability, it did apply to water and 1,4-dioxane in the 20 nm alumina membranes. Thermoporometry, coupled with permeability, was further used to evaluate surface wetting within the mesopores.
Permeation of carbon dioxide through microporous silica membranes at subcritical and supercritical conditions
The one-component transient permeation of carbon dioxide through an alumina-supported silica membrane is studied for pressures up to 2.0 × 107 Pa, at temperatures of 296, 313, and 358 K. The permeation is obtained for gaseous, liquid, and supercritical carbon dioxide. For all conditions high carbon dioxide fluxes were obtained. The membrane has been tested with a maximum pressure difference between the feed and the permeate side of about 2.5 × 106 Pa. At a feed-side pressure of 2.0 × 107 Pa and at 358 K the permeance is equal to 8.0 × 10-8 mol m-2 s-1 Pa-1. The transient transport through the microporous membrane can be described with a single mass-transfer coefficient. For a feed-side pressure between 1.0 × 105 and 200 × 105 Pa and a temperature of 296 K the mass-transfer coefficient increases by a factor of 80. The fact that carbon dioxide has a high flux through this type of silica membrane opens the way for regeneration of carbon dioxide at supercritical conditions.