Alumina diffusion models

Diffusion within the largest cavities of a porous medium is assumed to be similar to ordinary or bulk diffusion except that it is hindered by the pore walls (see Eq. 5-236). The tortuosity T that expresses this hindrance has been estimated from geometric arguments. Unfortunately, measured values are often an order of magnitude greater than those estimates. Thus, the effective diffusivity D f (and hence t) is normally determined by comparing a diffusion model to experimental measurements. The normal range of tortuosities for sihca gel, alumina, and other porous solids is 2 < T < 6, but for activated carbon, 5 < T < 65. 

Fig. 3. Shrinkage isotherms for high-purity alumina plotted according to the grain boundary diffusion model.

Fig. 5. Shrinkage isotherms for pure and titania-doped Linde Cl.O alumina plotted according to the volume diffusion model. T = 1300°C. Data from Bagley (12). 

In this paper we will first describe a fast-response infrared reactor system which is capable of operating at high temperatures and pressures. We will discuss the reactor cell, the feed system which allows concentration step changes or cycling, and the modifications necessary for converting a commercial infrared spectrophotometer to a high-speed instrument. This modified infrared spectroscopic reactor system was then used to study the dynamics of CO adsorption and desorption over a Pt-alumina catalyst at 723 K (450°C). The measured step responses were analyzed using a transient model which accounts for the kinetics of CO adsorption and desorption, extra- and intrapellet diffusion resistances, surface accumulation of CO, and the dynamics of the infrared cell. Finally, we will briefly discuss some of the transient response (i.e., step and cycled) characteristics of the catalyst under reaction conditions (i.e.,... 

All the experimental data in Table 6.1 refer to pure gases. Separation experiments, in which surface diffusion is the separation mechanism, are scarcely reported. Feng and Stewart (1973) and Feng, Kostrov and Stewart (1974) report multicomponent diffusion experiments for the system He-Nj-CH in a y-alumina pellet over a wide range of pressures (1-70 bar), temperatures (300-390 K) and composition gradients. A small contribution of surface diffusion (5% of total flow) to total transport could be detected, although it is not clear, which of the gases exhibits surface difiusion. The data could be fitted with the mass-flux model of Mason, Malinauskas and Evans (1967), extended to include surface diffusion. 

For the detailed study of reaction-transport interactions in the porous catalytic layer, the spatially 3D model computer-reconstructed washcoat section can be employed (Koci et al., 2006, 2007a). The structure of porous catalyst support is controlled in the course of washcoat preparation on two levels (i) the level of macropores, influenced by mixing of wet supporting material particles with different sizes followed by specific thermal treatment and (ii) the level of meso-/ micropores, determined by the internal nanostructure of the used materials (e.g. alumina, zeolites) and sizes of noble metal crystallites. Information about the porous structure (pore size distribution, typical sizes of particles, etc.) on the micro- and nanoscale levels can be obtained from scanning electron microscopy (SEM), transmission electron microscopy ( ), or other high-resolution imaging techniques in combination with mercury porosimetry and BET adsorption isotherm data. This information can be used in computer reconstruction of porous catalytic medium. In the reconstructed catalyst, transport (diffusion, permeation, heat conduction) and combined reaction-transport processes can be simulated on detailed level (Kosek et al., 2005). 

A classical example of this type of competitive reaction is the conversion of ethanol by a copper catalyst at about 300°C. The principal product is acetaldehyde but ethylene is also evolved in smaller quantities. If, however, an alumina catalyst is used, ethylene is the preferred product. If, in the above reaction scheme, B is the desired product then the selectivity may be found by comparing the respective rates of formation of B and C. Adopting the slab model for simplicity and remembering that, in the steady state, the rates of formation of B and C must be equal to the flux of B and C at the exterior surface of the particle, assuming that the effective diffusivities of B and C are equal ... 

The in situ diffuse reflectance FTIR studies were carried out on a Perkin Elmer (model 2000) instrument, including a diffuse reflection unit and a reaction chamber. The gas flow of 30 ml min"1 was passed through the reaction chamber, containing the catalyst on an alumina sample holder. The spectra were measured in the reflection mode, with 25 scans and 8 cm 1. 

Methyl chloride is an important industrial product, having a global annual capacity of ca. 900 000 tons. Its primary use is for the manufacture of more highly chlorinated materials such as dichloromethane and chloroform and for the production of silicone fluids and elastomers. It is usually manufactured by the reaction of methanol with hydrogen chloride with a suitable acid catalyst, such as alumina. To develop a site-specific reaction mechanism and a kinetics model for the overall process, one first needs to identify all the reagents present at the catalyst surface and the nature of their interactions with the surface. The first step in the reaction is dissociative adsorption of methanol to give adsorbed methoxy species. Diffuse reflectance IR spectroscopy (29d) showed the expected methoxy C-H stretch and deformations, but an additional feature, with some substructure, at 2600 cm was... 

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