Poisoning, catalyst deactivation from

Catalyst deactivation from a poisoning mechanism was most severe when lead alone was present in the fuel. Hence lead in the fuel may be... 

Catalyst contamination from sources such as turbine lubricant and boiler feed water additives is usuaUy much more severe than deactivation by sulfur compounds in the turbine exhaust. Catalyst formulation can be adjusted to improve poison tolerance, but no catalyst is immune to a contaminant that coats its surface and prevents access of CO to the active sites. Between 1986 and 1990 over 25 commercial CO oxidation catalyst systems operated on gas turbine cogeneration systems, meeting both CO conversion (40 to 90%) and pressure drop requirements. 

The space velocity was varied from 2539 to 9130 scf/hr ft3 catalyst. Carbon monoxide and ethane were at equilibrium conversion at all space velocities however, some carbon dioxide breakthrough was noticed at the higher space velocities. A bed of activated carbon and zinc oxide at 149 °C reduced the sulfur content of the feed gas from about 2 ppm to less than 0.1 ppm in order to avoid catalyst deactivation by sulfur poisoning. Subsequent tests have indicated that the catalyst is equally effective for feed gases containing up to 1 mole % benzene and 0.5 ppm sulfur (5). These are the maximum concentrations of impurities that can be present in methanation section feed gases. 

Catalyst deactivation refers to the loss of catalytic activity and/or product selectivity over time and is a result of a number of unwanted chemical and physical changes to the catalyst leading to a decrease in number of active sites on the catalyst surface. It is usually an inevitable and slow phenomenon, and occurs in almost all the heterogeneous catalytic systems.111 Three major categories of deactivation mechanisms are known and they are catalyst sintering, poisoning, and coke formation or catalyst fouling. They can occur either individually or in combination, but the net effect is always the removal of active sites from the catalyst surface. 

Stefanov and coworkers—deactivation pathways for industrial Cu/Cr/Zn catalysts. Stefanov and coworkers250 published an XPS study indicating that the Cu-Cr-Zn catalyst deactivates via two pathways in an industrial reactor-sintering and poisoning by chlorine adsorption, which caused a deactivation of the catalyst from... 

There are numerous indications in the literature on catalyst deactivation attributed to over-oxidation of the catalyst (3-5). In the oxidative dehydrogenation of alcohols the surface M° sites are active and the rate of oxygen supply from the gas phase to the catalyst surface should be adjusted to that of the surface chemical reaction to avoid "oxygen poisoning". The other important reason for deactivation is the by-products formation and their strong adsorption on active sites. This type of... 

The persistence of the dendrimer decomposition products is the likely cause of the catalyst deactivation over time. The presence of dendrimer and dendrimer byproducts indicates that even the more active catalysts are not particularly clean. It is difficult to distinguish between species adsorbed on the NPs from those primarily on the support however, it is likely that the location of the dendrimer decomposition varies widely along the surface of the catalyst. The dendrimer fragments present on the support could migrate over time and poison the metal active sites, resulting in the lower catalytic activity over time. It is also possible that the residual dendrimer undergoes some slower oxidation processes that result in a stronger, unobservable poison. 

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).

There is no evidence in vehicle operation that the oxidation activity of noble metal catalysts suffers from poisoning by SOz (24, 28, 84), although Hunter claims (43) that Pt can be poisoned below 900°F. In contrast, severe deactivation of base metal catalysts has been observed in many instances. 

In the actual process (Figure 10-5), the natural gas feedstock must first be desulfurized in order to prevent catalyst poisoning or deactivation. The desulfurization step depends upon the nature of the sulfur-containing contaminants and can vary from the more simple ambient temperature adsorption of the sulfur-containing materials on activated charcoal to a more complex high-temperature reaction with zinc oxide to catalytic hydrogenation followed by zinc oxide treatment. 

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