Aging activity, catalyst

Fig. 6. Catalyst inhibition mechanisms where ( ) are active catalyst sites the catalyst carrier and the catalytic support (a) masking of catalyst (b) poisoning of catalyst (c) thermal aging of catalyst and (d) attrition of ceramic oxide metal substrate monolith system, which causes the loss of active catalytic material resulting in less catalyst in the reactor unit and eventual loss in performance.

In other instances, reaction kinetic data provide an insight into the rate-controlling steps but not the reaction mechanism see, for example, Hougen and Watson s analysis of the kinetics of the hydrogenation of mixed isooctenes (16). Analysis of kinetic data can, however, yield a convenient analytical insight into the relative catalyst activities, and the effects of such factors as catalyst age, temperature, and feed-gas impurities on the catalyst. 

Several previous studies have demonstrated the power of AEH in various catalyst systems (1-11). Often AEM can provide reasons for variations in activity and selectivity during catalyst aging by providing information about the location of the elements involved in the active catalyst, promoter, or poison. In some cases, direct quantitative correlations of AEM analysis and catalyst performance can be made. This paper first reviews some of the techniques for AEM analysis of catalysts and then provides some descriptions of applications to bismuth molybdates, Pd on carbon, zeolites, and Cu/ZnO catalysts. 

We found highly active catalysts, which are shown in Table I (3). The main component is a stable carboxylate of uranium in the oxidation state of +4, in combination with a Lewis acid and an aluminum alkyl, e.g. uranium octoate, aluminum tribromide, and triisobutylaluminum in a molar ratio of 1 0.8 25. The catalyst is usually aged for at least 2 hours at room temperature. 

Col I(CN)-, 1 is readily formed under mild conditions from Co(CN)2, KCN and H2 [Eqs. (1) and (2)]. It is an active catalyst for the hydrogenation of a variety of unsaturated substrates, and in fact in the first documented examples of two-phase hydrogenations this catalyst was used [48, 49]. The catalysis suffers from several drawbacks such as rapid aging with a loss of activity, and the need to use highly basic aqueous solutions. 

As discussed above, the potential octane boost which can be achieved from ZSM-5 addition is a function of five parameters the regenerator temperature and steam partial pressure (which determine the activity maintenance) the base and ZSM-5 catalyst makeup rates (which determine the catalyst age) and the base gasoline octane. The sensitivity of the model to these parameters is discussed below. 

Probably the major problem in designing the ACC is the maintenance of activity as the catalyst ages (law requires performance within tight specifications to at least 50,000 miles). Rapid activation of the cold catalyst in startup is related to aging because the inactive catalyst generates less heat. 

Carbon supported powdered palladium catalysts have been widely used in the chemical industry. In addition to activity and selectivity of those catalysts, the recovery rate of the incorporated precious metal has a major impact on the economic performance of the catalyst. In this study, the effects of catalyst age, oxidation state of the incorporated metal and temperature treatment on the palladium leaching resistance as well as on activity and dispersion of carbon supported palladium catalysts were investigated. 

The EM studies show that the novel glide shear mechanism in the solid state heterogeneous catalytic process preserves active acid sites, accommodates non-stoichiometry without collapsing the catalyst bulk structure and allows oxide catalysts to continue to operate in selective oxidation reactions (Gai 1997, Gai et al 1995). This understanding of which defects make catalysts function may lead to the development of novel catalysts. Thus electron microscopy of VPO catalysts has provided new insights into the reaction mechanism of the butane oxidation catalysis, catalyst aging and regeneration. 

As the catalyst ages, the rate constants decrease since the number of active sites is reduced by coke formation ... 

These deposits responsible for fouling can block out the reactants and prevent them from reaching the active sites, or even block the internal pores of the catalyst. Hydrocarbons and aromatics are usually the cause of coking. The chemical nature of the carbonaceous deposits relies on many parameters temperature, pressure, feed composition, nature of products, and catalyst age share the responsibility of the residue formation on catalysts. 

Longer on-stream time, due to the ability to control any decline of catalyst activity with age by periodic additions of fresh catalyst. 

Activities were measured between 75° and 110°C with zeolitic catalysts and between 120° and 170°C with conventional ones for both series the experimental results were extrapolated to give the activity at 140° C. Little catalyst aging was observed in these working conditions (<10% in two hours) the reproducibility of the experiments was better than 10%. 

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