Anna A. Lysova

Monitoring Transport Phenomena of Paramagnetic Metal‐Ion Complexes Inside Catalyst Bodies with Magnetic Resonance Imaging

An indirect magnetic resonance imaging (MRI) method has been developed to determine in a noninvasive manner the distribution of paramagnetic Co2+ complexes inside Co/Al2O3 catalyst extrudates after impregnation with Co2+/citrate solutions of different pH and citrate concentrations. UV/Vis/NIR microspectroscopic measurements were carried out simultaneously to obtain complementary information on the nature of the Co2+ complexes. In this way, it could be confirmed that the actual distribution of Co2+ inside the extrudates could be derived from the MRI images. By combining these space- and time-resolved techniques, information was obtained on both the strength and the mode of interaction between [Co(H2O)6]2+ and different Co2+ citrate complexes with the Al2O(3) support. Complexation of Co2+ by citrate was found to lead to a stronger interaction of Co with the support surface and formation of an eggshell distribution of Co2+ complexes after impregnation. By addition of free citrate and by changing the pH of the impregnation solution, it was possible to obtain the rather uncommon egg-yolk and egg-white distributions of Co2+ inside the extrudates after impregnation. In other words, by carefully altering the chemical composition and pH of the impregnation solution, the macrodistribution of Co2+ complexes inside catalyst extrudates could be fine-tuned from eggshell over egg white and egg yolk to uniform.

Magnetic Resonance Imaging Studies on Catalyst Impregnation Processes: Discriminating Metal Ion Complexes within Millimeter-Sized γ-Al2O3 Catalyst Bodies

Magnetic resonance imaging (MRI) was used to study the impregnation step during the preparation of Ni/gamma-Al(2)O(3) hydrogenation catalysts with Ni(2+) metal ion present in different coordinations. The precursor complexes were [Ni(H(2)O)(6)](2+) and [Ni(edtaH(x))]((2-x)-) (where x = 0, 1, 2 and edta = ethylenediaminetetraacetic acid), representing a nonshielded and a shielded paramagnetic complex, respectively. Due to this shielding effect of the ligands, the dynamics of [Ni(H(2)O)(6)](2+) or [Ni(edtaH(x))]((2-x)-) were visualized applying T(2) or T(1) image contrast, respectively. MRI was applied in a quantitative manner to calculate the [Ni(H(2)O)(6)](2+) concentration distribution after impregnation when it was present alone in the impregnation solution, or together with the [Ni(edtaH(x))]((2-x)-) species. Moreover, the combination of MRI with UV-vis microspectroscopy allowed the visualization of both species with complementary information on the dynamics and adsorption/desorption phenomena within gamma-Al(2)O(3) catalyst bodies. These phenomena yielded nonuniform Ni distributions after impregnation, which are interesting for certain industrial applications.

Spatially resolved NMR thermometry of an operating fixed-bed catalytic reactor.

An MRI-based approach for the thermometry of an operating packed-bed catalytic reactor was implemented. It was employed for the spatially resolved NMR thermometry of the bed of Pd/gamma-Al2O3 catalyst beads in the course of propylene hydrogenation reaction. This was achieved by detecting the spatially resolved axial 1D profiles of the 27Al NMR signal intensity of Al2O3 in the course of the reaction. The experimental results demonstrate a clear correlation between the 27Al NMR signal intensity and the catalyst temperature measured with a thermocouple (25-250 degrees C), and reveal the existence of pronounced temperature gradients along the catalyst bed.

The NMR microimaging studies of the interplay of mass transport and chemical reaction in porous media.

PFG NMR is employed to perform a comparative study of the filtration of water and propane through model porous media. It is shown that the dispersion coefficients for water are dominated by the holdup effects even in a bed of nonporous glass beads. It is demonstrated that correlation experiments such as VEXSY are applicable to gas flow despite the large diffusivity values of gases. The PFG NMR technique is applied to study the gravity driven flow of liquid-containing fine solid particles through a porous bed. The NMR imaging technique is employed to visualize the propagation of autocatalytic waves for the Belousov-Zhabotinsky reaction which is carried out in a model porous medium. It is demonstrated that the wave propagation velocity decreases as the wave crosses the boundary between the bulk liquid and the flooded bead pack. The images detected during the catalytic hydrogenation of alpha-methylstyrene on a single catalyst pellet at elevated temperatures have revealed that the reaction and the accompanying phase transition alter the distribution of the liquid phase within the pellet.

Quantitative temperature mapping within an operating catalyst by spatially resolved 27Al NMR.

Spatially resolved NMR is employed to quantitatively map the temperature of a solid catalyst under operating conditions during H(2) oxidation with O(2) over Pt/γ-Al(2)O(3). As this new non-invasive in situ technique utilizes the (27)Al NMR signal of the solid phase, it is suitable for catalyst temperature mapping in both liquid- and gas-phase heterogeneous catalytic processes.