Washcoat distribution

The problem of reaction diffusion in square channels with a nonuniform washcoat distribution in two spatial dimensions can be solved numerically using, e.g., the finite element method, as illustrated by Hayes and Kolaczkowski [22]. 

Exemplary results of modeling processes inside the catalytic layer are presented in Fig. 9. The solid lines show the dependency of the overall effectiveness factor on the relative distribution of the catalyst between the comers and the side regions. The two cases represent two levels of the first-order rate constants, with the faster reaction in case (b). As expected, the effectiveness factor of the first reaction drops as more catalyst is deposited in the comers. The effectiveness factor for the second reaction increases in case (a) but decreases in case (b). The latter behavior is caused by depletion of B deep inside the catalytic layer. What might be surprising is the rather modest dependency of the effectiveness factor on the washcoat distribution. The explanation is that internal diffusion is not important for slow reactions, while for fast reactions the available external surface area becomes the key quantity, and this depends only slightly on the washcoat distribution for thin layers. The dependence of the effectiveness factor on the distribution becomes more pronounced for consecutive reactions described by Langmuir-Hinshelwood-Hougen-Watson kinetics [26]. 

For the TBR, spherical catalyst particles of uniform size with the catalytically active material either uniformly distributed throughout the catalyst or present in a shell were considered. For the MR, channels of square cross section were assumed to have walls covered by the washcoat distributed in such a way that the comers are approximated by the circle-in-square geometry, while the sides are approximated by a planar slab geometry. The volumetric load of catalytic material was a function of the washcoat thickness... 

Diffusion effects can be expected in reactions that are very rapid. A great deal of effort has been made to shorten the diffusion path, which increases the efficiency of the catalysts. Pellets are made with all the active ingredients concentrated on a thin peripheral shell and monoliths are made with very thin washcoats containing the noble metals. In order to convert 90% of the CO from the inlet stream at a residence time of no more than 0.01 sec, one needs a first-order kinetic rate constant of about 230 sec-1. When the catalytic activity is distributed uniformly through a porous pellet of 0.15 cm radius with a diffusion coefficient of 0.01 cm2/sec, one obtains a Thiele modulus y> = 22.7. This would yield an effectiveness factor of 0.132 for a spherical geometry, and an apparent kinetic rate constant of 30.3 sec-1 (106). 

Also a simulation of the flow field in the methanol-reforming reactor of Figure 2.21 by means of the finite-volume method shows that recirculation zones are formed in the flow distribution chamber (see Figure 2.22). One of the goals of the work focused on the development of a micro reformer was to design the flow manifold in such a way that the volume flows in the different reaction channels are approximately the same [113]. In spite of the recirculation zones found, for the chosen design a flow variation of about 2% between different channels was predicted from the CFD simulations. In the application under study a washcoat cata-... 

The following, well-acceptable assumptions are applied in the presented models of automobile exhaust gas converters Ideal gas behavior and constant pressure are considered (system open to ambient atmosphere, very low pressure drop). Relatively low concentration of key reactants enables to approximate diffusion processes by the Fick s law and to assume negligible change in the number of moles caused by the reactions. Axial dispersion and heat conduction effects in the flowing gas can be neglected due to short residence times ( 0.1 s). The description of heat and mass transfer between bulk of flowing gas and catalytic washcoat is approximated by distributed transfer coefficients, calculated from suitable correlations (cf. Section III.C). All physical properties of gas (cp, p, p, X, Z>k) and solid phase heat capacity are evaluated in dependence on temperature. Effective heat conductivity, density and heat capacity are used for the entire solid phase, which consists of catalytic washcoat layer and monolith substrate (wall). 

Mass and heat transfer between flowing gas and catalytic washcoat layer along the monolith channel are in ID gas models approximated by distributed... 

Porous catalytic washcoat exhibits bimodal pore size distribution with larger macropores (rp 100-500 nm) among individual support material particles (e.g. - , zeolites), and small meso-/micropores (rp 3-6nm) inside the particles. Typical pore size distribution and electron microscopy images of y-A C -based washcoat can be found, e.g. in Stary et al. (2006) and Koci et al. 

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). 

Stabilizers can be introduced into the pellets or the washcoats with the intention of slowing down the thermally induced decrease in the surface area of the porous structure itself, or of the active component. Both, the active materials and the stabilizers, are put sometimes only on the outer layers of the pellets or monoliths, while, in other cases they penetrate the porous structures completely. Such preferential distributions have very specific aims, the utilization of the active materials and their protection from poisoning being the most important ones. There exists a vast body of patent literature on such designs. 

Complete characterization of poisoned catalysts, of course, requires much more than chemical analysis. For example, the interaction of poisons with catalyst constituents and with each other has been studied by X-ray diffraction and by electron microscopy, the morphology of the poison deposits by optical methods, the distribution within the catalyst pellets and washcoats by the microprobe, and the distribution of poison on the surface of the active metals by Auger spectroscopy. 

The macro-porosity emacro and the correlation function corresponding to the macro-pore size distribution of the washcoat were evaluated from the SEM images of a typical three-way catalytic monolith, cf. Fig. 25. The reconstructed medium is represented by a 3D matrix and exhibits the same porosity and correlation function (distribution of macro-pores) as the original porous catalyst. It contains the information about the phase at each discretization point— either gas (macro-pore) or solid (meso-porous Pt/y-Al203 particle). In the first approximation, no difference is made between y-Al203 and Ce02 support, and the catalytic sites of only one type (Pt) are considered with uniform distribution. 

The results of the parametric studies (e.g., the influence of noble metal distribution and correlation length) provide a better understanding of the reaction-transport effects in porous, supported heterogeneous catalysts (Bhattacharya et al., 2004). In the combination with semi-deterministic methods of the reconstruction (simulation of the catalyst preparation process), the results can be used for the optimization of the washcoat structure. 

Considerations along the above lines lead to analogous correlations for the Sherwood number for the description of mass transfer in a single channel. The application of the rather simple Nusselt and Sherwood number concept for monolith reactor modeling implies that the laminar flow through the channel can be approached as plug flow, but it is always limited to cases in which homogeneous gas-phase reactions are absent and catalytic reactions in the washcoat prevail. If not, a model description via distributed flow is necessary. 

The thickness of the catalytic layer deposited on channel walls is very small The average varies typically from 10 to 150 p,m. The first approximation concerning the deposit distribution is that the layer is distributed uniformly around the channel periphery. This may be true if circular channels are considered. The typical cross section of the monolith channels is, however, square. In this case a significant nonuniformity in the washcoat thickness is often encountered (Fig. 6). The reason is that the liquid from which the... 

Figure 6 Nonuniform distribution of washcoat on a monolith. (From Ref. 22.)...

The pore sice distribution of UNSWAL before and after thermal treatment at lOOO C is shown In Figure 12, Stich a pore elze distribution appears to be suitable for washcoat preparation. 

Fig. 1(B) shows a schematic representation of a gas turbine fitted with a catalytic combustor. The entire air stream from the compressor is mixed with fuel and fed to the combustor. The adiabatic temperature of this mixture is 1300°C, therefore, the combustor exhaust gases are fed to the power turbine directly and without further dilution. Fuel is uniformly distributed over the cross-section of the combustor and mixed with air upstream of the catalyst. The catalyst is most frequently dispersed within a washcoat coated onto the surface of a monolith to minimize pressure losses and intraparticle transport restrictions.

Fig. 4 Axial temperature and methane conversion distributions in a catalytic combustor calculated by solving Eqs. (1), (2), and (5) for the conditions presented in Table 1. The maximum washcoat temperature is obtained at the monolith inlet, where both gas temperature and fuel conversion are very low. Shortening the monolith would result in lower gas outlet temperatures and incomplete fuel conversion, but washcoat temperatures will remain unchanged. (View this art in color at www.dekker.com.)...

The precious metal composition is typically uniform in the radial and axial directions of the monolith structure, although different designs have been described in the patent literature and have even been used in some selected applications. However, much more common is a nonuniform distribution of the precious metals within the washcoat layer. One - macroscopic - example of nonuniform distribution is that the amount of one precious metal component decreases from the part of the washcoat that is in contact with the gas phase towards the part of the washcoat that is in contact with the monolith wall and eventually vice-versa for the second precious metal component. Another - microscopic - example of nonuniform distribution within the washcoat is that each precious metal component is selectively deposited on different washcoat components. These nonuniformities are intentional and are desirable for kinetic reasons or because of specific beneficial interactions between the precious metals and the washcoat oxides. The type of nonuniformity that can be achieved depends strongly on the production procedure of the catalyst. 

Within a single secondary washcoat particle, the distribution of the precious metals can be assumed to be relatively homogeneous. The precious metals are typically present in a highly dispersed state. Dispersions measured by CO chemisorption methods are typically in the range 10-50% or even higher, for fresh catalysts. This means that the precious metals are present as single atoms or as small clusters of about ten atoms. For a catalyst with about 1.8 g precious metal per liter of catalyst volume, this corresponds to a precious metal surface area in the range of about 3-30 m 1 catalyst volume. 

Figure 65. Effect of the gas to washcoat heat transfer rate on the distribution of solids temperature over the radius of a ceramic monolith at its outlet frontal area, for a washcoat with a high heat transfer rate (C2) and for a washcoat with a low heat transfer rate (Cl). Reprinted with permission from ref [34], 1991 Society of Automotive Engineers, Inc.

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