Diffusion-Deactivation

For batch 5/plug flow G integration of the various diffusion deactivation regimes gives the values in Table 21.1. 

A further observation which may be made is that a large part of the nickel must remain in the form of unreduced nickel oxide or must be in subdomain particle size region. This must be true because the total magnetization observed is only about 5 per cent of that expected for an equivalent weight of nickel metal. It is well known that the most active catalysts of the type described are prepared by long reduction at quite moderate temperatures. A possible reason for this is that if the temperature is too high, rapid diffusion deactivates the catalyst. But if the temperature is low, long times are necessary to obtain appreciable reduction. 

Chemical deactivation coking. See Coking dependent, 151, 177 diffusion-deactivation, 164 fouling, 151 independent, 151, 156 kinetics of, 155 nature of, 152 poisoning, 151 shell-progressive, 164, 167 uniform, 164 Coarsening, 201 Coking... 

Do we expect this model to be accurate for a dynamics dictated by Tsallis statistics A jump diffusion process that randomly samples the equilibrium canonical Tsallis distribution has been shown to lead to anomalous diffusion and Levy flights in the 5/3 < q < 3 regime. [3] Due to the delocalized nature of the equilibrium distributions, we might find that the microstates of our master equation are not well defined. Even at low temperatures, it may be difficult to identify distinct microstates of the system. The same delocalization can lead to large transition probabilities for states that are not adjacent ill configuration space. This would be a violation of the assumptions of the transition state theory - that once the system crosses the transition state from the reactant microstate it will be deactivated and equilibrated in the product state. Concerted transitions between spatially far-separated states may be common. This would lead to a highly connected master equation where each state is connected to a significant fraction of all other microstates of the system. [9, 10]... 

Oral adrninistration of vacciaes may be ineffective as many vacciaes are deactivated in the digestive tract of the animals the vacciaes are intended to protect. Dip treatment by which the vacciaes enter the animals through diffusion from the water are not generally as effective as injection but can be used to vaccinate large numbers of animals in short periods of time. 

The metal surface area at the inlet end of the catalyst bed in experiment HGR-12 was smaller than that at the outlet end this indicates that a decrease in nickel metal sites is part of the deactivation process. Sintering of the nickel is one possible mechanism, but carbon and carbide formation are suspected major causes. Loss of active Raney nickel sites could also conceivably result from diffusion of residual free aluminum from unleached catalyst and subsequent alloying with the free nickel to form an inactive material. 

First, in composites with high fiber concentrations, there is little matrix in the system that is not near a fiber surface. Inasmuch as polymerization processes are influenced by the diffusion of free radicals from initiators and from reactive sites, and because free radicals can be deactivated when they are intercepted at solid boundaries, the high interfacial area of a prepolymerized composite represents a radically different environment from a conventional bulk polymerization reactor, where solid boundaries are few and very distant from the regions in which most of the polymerization takes place. The polymer molecular weight distribution and cross-link density produced under such diffusion-controlled conditions will differ appreciably from those in bulk polymerizations. 

Reaction, diffusion, and catalyst deactivation in a porous catalyst layer are considered. A general model for mass transfer and reaction in a porous particle with an arbitrary geometry can be written as follows ... 

Organosilanes, especially dimethyldichlorosilane (M2), are important chemicals used in the silicone industries. The direct reaction of silicon with an organic halide to produce the corresponding organosilanes as a gas-solid-solid catalytic reaction was first disclosed by Rochow [1]. In the reaction, a copper-containing precursor first reacts with silicon particles to form the catalytically active component, which is a copper-silicon alloy, the exact state of which is still under discussion. As the reaction proceeds. Si in the alloy is consumed, which is followed by the release of copper. This copper diffuses into the Si lattice to form new reaction centers until deactivation occurs. The main reaction of the direct process is ... 

The selectivity in a system of parallel reactions does not depend much on the catalyst size if effective diffusivities of reactants, intermediates, and products are similar. The same applies to consecutive reactions with the product desired being the final product in the series. In contrast with this, for consecutive reactions in which the intermediate is the desired product, the selectivity much depends on the catalyst size. This was proven by Edvinsson and Cybulski (1994, 1995) for. selective hydrogenations and also by Colen et al. (1988) for the hydrogenation of unsaturated fats. Diffusion limitations can also affect catalyst deactivation. Poisoning by deposition of impurities in the feed is usually slower for larger particles. However, if carbonaceous depositions are formed on the catalyst internal surface, ageing might not depend very much on the catalyst size. 

The analysis carried out allows us to state the general conditions needed to properly determine the coefficient of heterogeneous deactivation by the diffusion method ... 

Because of these factors, the fundamental experimental information about the interaction of metastable atoms with semiconductors and dielectrics is meant for the reflection coefficients that are determined with the aid of beam methods and for the coefficients of heterogeneous deactivation which are evaluated under diffusion conditions. However, the data in this event are fairly scarce and conflicting. The results obtained by the methods of electronic beams do not agree with diffusion experiments. Thus, Allison et al [ 137] report that the coefficients dealing with... 

J. Wood, L. F. Gladden 2003, (Effect of coke deposition upon pore structure and self-diffusion in deactivated industrial hydroprocessing catalysts), Appl.Cat. A General, 249, 241. 

The hydrogenation of para-substituted anilines over rhodium catalysts has been investigated. An antipathetic metal crystallite size effect was observed for the hydrogenation of /Moluidinc suggesting that terrace sites favour the reaction. Limited evidence was found for catalyst deactivation by the product amines. Catalysts with pore diameters less than 13.2 nm showed evidence of diffusion control on the rate of reaction but not the cis trans ratio of the product. 

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