Deactivation examples

There are some other process problems, which are frequently mistaken as catalyst deactivation. Examples are metal and ore deposition, scale formation and polymerization at the top of the catalyst bed. The catalyst has to be replaced when the severity has reached the design specifications of the unit or when an increase in severity does not compensate adequately the lost of activity. 

Lipid-soluble hormones act usually by gene activation/deactivation. Examples of these hormones include steroids, thyroid hormone, and vitamin A (retinoic acid). The hormones are transported through the circulation in association with a hormone-binding protein and are soluble in the plasma membrane of the cell. Their receptors are intracellular, and they act on gene transcription (the synthesis of messenger RNA) rather than at the protein level. Thus, they act more slowly than do the soluble hormones, on the scale of days rather than minutes. 

Fu et al. developed a room temperature, photoinduced, copper-catalyzed C—N Ullmarm coupling of electrophiles with nitrogen heterocycles (229- 231).The scope of allowed electrophiles is quite broad aryl halides, including hindered and deactivated examples, alkenyl halides, and alkynyl bromides are all tolerated. Indoles, benzimidazoles, and imidazoles can all undergo C-N coupling (13JA13107). 

An important example for the application of general first-order kinetics in gas-phase reactions is the master equation treatment of the fall-off range of themial unimolecular reactions to describe non-equilibrium effects in the weak collision limit when activation and deactivation cross sections (equation (A3.4.125)) are to be retained in detail [ ]. 

The pyridine-like nitrogen of the 2H-pyrrol-2-yiidene unit tends to withdraw electrons from the conjugated system and deactivates it in reactions with electrophiles. The add-catalyzed condensations described above for pyrroles and dipyrromethanes therefore do not occur with dipyrromethenes. Vilsmeier formylation, for example, is only successful with pyrroles and dipyrromethanes but not with dipyrromethenes. 

Returning to Table 12 2 notice that halogen substituents direct an incoming electrophile to the ortho and para positions but deactivate the ring toward substitution Nitration of chlorobenzene is a typical example of electrophilic aromatic substitution m a halobenzene... 

Aluminum chloride is a stronger Lewis acid than iron(lll) bromide and has been used as a catalyst in electrophilic bromination when as in the example shown the aromatic ring bears a strongly deactivating substituent... 

Amorphous Silica—Alumina Based Processes. Amorphous siHca—alumina catalysts had been used for many years for xylene isomerization. Examples ate the Chevron (130), Mamzen (131), and ICI (132—135). The primary advantage of these processes was their simpHcity. No hydrogen was requited and the only side reaction of significance was disproportionation. However, in the absence of H2, catalyst deactivation via coking... 

Many forms of chromatography have been used to separate mixtures of quinoline and isoquinoline homologues. For example, alumina saturated with cobalt chloride, reversed-phase Hquid chromatography, and capillary gas chromatography (gc) with deactivated glass columns have all been employed (38,39). 

Metal Deactivation. Compounds capable of forming coordination complexes with metal ions are needed for this purpose. A chelating agent such as ethylene-diaminetetraacetic acid (EDTA) is a good example. 

Examples of commercial metal deactivators used in polymers, gasoline, and foods are oxalyl bis(bensyhdene)hydraside [6629-10-3] (28). 

Catalyst Deactivation. Catalyst deactivation (45) by halogen degradation is a very difficult problem particularly for platinum (PGM) catalysts, which make up about 75% of the catalysts used for VOC destmction (10). The problem may weU He with the catalyst carrier or washcoat. Alumina, for example, a common washcoat, can react with a chlorinated hydrocarbon in a gas stream to form aluminum chloride which can then interact with the metal. Fluid-bed reactors have been used to offset catalyst deactivation but these are large and cosdy (45). 

By deactivating the active weak link. For example, commercial polyacetal (polyformaldehyde) resins have their chain ends capped by a stable grouping. (This will, however, be of little use where the initiation of chain degradation is not at the terminal group.)... 

Effect of Pressure Figure 3 shows the effect of pressure on product sulfur. In the 400-800 psig range, doubling the pressure reduces the product sulfur by about one third. Pressure also has an effect on catalyst life. In general, as the pressure is increased the catalyst deactivates at a lower rate. However, beyond a certain point, further increases in pressure have only a small effect on deactivation rate. An example of this is for atmospheric resids typical data... 

Similar approaches are applicable in the chemical industry. For example, maleic anhydride is manufactured by partial oxidation of benzene in a fixed catalyst bed tubular reactor. There is a potential for extremely high temperatures due to thermal runaway if feed ratios are not maintained within safe limits. Catalyst geometry, heat capacity, and partial catalyst deactivation have been used to create a self-regulatory mechanism to prevent excessive temperature (Raghaven, 1992). 

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