Catalyst deactivation particle size effect

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. 

Batchwise operating three-phase reactors are frequently used in the production of fine and specialty chemicals, such as ingredients in drags, perfumes and alimentary products. Large-scale chemical industry, on the other hand, is often used with continuous reactors. As we developed a parallel screening system for catalytic three-phase processes, the first decision concerned the operation mode batchwise or continuous. We decided for a continuous reactor system. Batchwise operated parallel sluny reactors are conunercially available, but it is in many cases difficult to reveal catalyst deactivation from batch experiments. In addition, investigation of the effect of catalyst particle size on the overall activity and product distribution is easier in a continuous device. 

In terms of the effect of water on the deactivation, several mechanisms have been identified, and they will influence the stability of the catalyst depending on the conditions and the support used. At high partial pressures of water oxidation is always a possibility, but the various reports are less clear to whether this is mainly surface oxidation of cobalt particles irrespective of particle size, or if small particles... 

Fig. 12. Effect of self-poisoning (i hr at 450 C, by the reaction mixture) on hexane/H2 reactions. AT is the temperature increase necessary to achieve the same overall conversion after poisoning over that before poisoning. AT is plotted as a function of the average particle size of various Pt/SiO2 catalysts. From V. Ponec et al, in Catalyst Deactivation, p. 93, Elsevier, Amsterdam (1980).

Industrially, catalyst activity maintenance is often screened via "temperature increase requirement" (TIR) experiments. In these experiments, constant conversion is established and the rate of temperature increase required to do so is used as a measure of the resistance of the catalyst to deactivation. However, this type of operation may mask the effect of particle size, temperature, temperature profile, and heat of reaction on poison coverage, poison profile, and the main reaction rate. This masking may be particularly important in complicated reactions and reactor systems where the TIR experiment may produce positive feedback. 

Pore size. The pore size distribution of the catalyst matrix plays a key role in the catalytic performance of the catalyst. An optimum pore size distribution usually helps in a balanced distribution of smaller and larger pores, and depends on feedstock type and cracking conditions. The pore size distribution of the matrix changes when another component is added e.g. by adding 35-40% kaolin to a silica-alumina gel, a pore structure with a significant amount of micropores can be obtained. Figure 27.9 Pore volume. Pore volume is an indication of the quantity of voids in the catalyst particles and can be a clue in detecting the type of catalyst deactivation that takes place in a commercial unit. Hydrothermal deactivation has very little effect on pore volume, whereas thermal deactivation decreases pore volume. 

Studies of catalysts deactivation by coke are abundant in the literature most of them are usually conducted at high temperatures (around 500°C) using metal catalysts supported on oxides with low surface area such as silica, aluminas or silica-alumina [2 and references therein]. The deactivation by coke of zeolite catalysts has also been studied and such studies have mostly been done for high temperature reactions such as the conversion of n-hexane or the isomerization of xylenes [2,4]. However, low temperature coke formation (20-25°C) combining the effect of high acidity and size specificity for a high coking component such as nickel, has not yet been considered from the point of view of the presence of compounded effects of crystalline structure and location of metal particles. 

The present work reports a promoting effect of the CeQ gZro 4O2 mixed oxide on the catalytic reduction of NO by CO at moderate temperatures. This effect is attributed to the Ce4+/Ce3+ redox couple which efficiently reduces NO. The interaction of the Pd/Ceo.gZro 4O2-AI2O3 catalysts with H2 reveals that considerable metal particle encapsulation occurs after a high temperature reduction. This suggests that the choice of an appropriate metal particle size may be an important factor to avoid the catalyst deactivation. Finally, a methodology for the determination of the H/Pd ratios is discussed. 

As metal concentration is increased particle size may increase, so support interactions will decrease. Variations in particle size are also associated with changes in the density of active sites, with associated effects on the catalysis. The concentration of the noble metal can affect both catalytic activity and resistance to deactivation, hence the amount of noble metal on a supported catalyst is of prime importance. The former is illustrated by Skoglundh [34], who noted that the overall noble metal content of a Pt-Pd catalyst (ratio 4/1) is of vital importance in determining the light off temperature for xylene oxidation, as the light off temperature markedly decreased as noble metal content increased in the range 5-20 pg mol These results are shown in figure 4. 

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