Deactivation mechanism, heterogeneous

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. 

During the operational lifetime of most catalysts, their activity decreases. Interestingly, the time period of economic operation can be very different even for commercial catalysts and ranges from a couple of seconds to many years. Table 2.3.8 gives an overview of some important heterogeneous catalyzed reactions, their reaction conditions, deactivation mechanism, possible regeneration options, and lifetime. It can be seen from the table that there is no direct correlation between thermal stress and lifetime. 

The catalyst deactivates, but after four runs the conversion is still significantly higher (> 99% after 2 h) as compared with the uncatalyzed reaction. Moreover, the Z-selectivity in all four runs is higher than 80%, whereas in the uncatalyzed reaction, it is typically only 30% (Z). The fact that the solid powder can be used several times furthermore supports the fact that the reaction mechanism is heterogeneous. The reason for the deactivation is unknown. A disadvantage of the nanoparticles is the difficulty of separation. Thus, in some cases the particles form col-... 

Being an integral magnitude, the heterogeneous deactivation coefficient does not allow us to judge of the particular mechanisms of EEP... 

An important role in the mechanism is plaid by the applied particles of metal. One can conclude so from the experiments in studying heterogeneous deactivation of RGMAs on a pure and Au microcrystal-activated surfaces of glass and zinc oxide [162], The experiments were conducted by the Smith method, Au/ZnO sensors being used as RGMA detectors. The results of these investigations are tabulated in Tables 5.3. 

The Elovich model was originally developed to describe the kinetics of heterogeneous chemisorption of gases on solid surfaces [117]. It describes a number of reaction mechanisms including bulk and surface diffusion, as well as activation and deactivation of catalytic surfaces. In solid phase chemistry, the Elovich model has been used to describe the kinetics of sorption/desorption of various chemicals on solid phases [23]. It can be expressed as [118] ... 

When gum formation proceeds, the minimum temperature in the catalyst bed decreases with time. This could be explained by a shift in the reaction mechanism so more endothermic reaction steps are prevailing. The decrease in the bed temperature speeds up the deactivation by gum formation. This aspect of gum formation is also seen on the temperature profiles in Figure 9. Calculations with a heterogenous reactor model have shown that the decreasing minimum catalyst bed temperature could also be explained by a change of the effectiveness factors for the reactions. The radial poisoning profiles in the catalyst pellets influence the complex interaction between pore diffusion and reaction rates and this results in a shift in the overall balance between endothermic and exothermic reactions. 

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