Catalyst poisoning results

Extensive catalyst poisoning results from the deposition of carbon in or on the catalyst surface. In technological parlance, this is usually referred to as the formation of coke. At temperatures in excess of those normally used for catalysis, hydrocarbon decomposition at metal surfaces is known... 

A common thread that can link the ammonium and peptone catalyst poisoning results just described could be the Maillard reactions of amino acids with sugars (5). Recent studies have shown that the ammonium ion is highly reactive, more so than substituted versions (6). Its use as ammonium bicarbonate in developing flavoring compounds by Maillard reactions in extrusion cookers has been reported (7). It is likely that such reactions could occur at our processing conditions. We can speculate that such products could have acted as catalyst surface poisons, which might have been subsequently washed from the catalyst, before it was reused in its active form. 

Inhibition, or catalyst poisoning, results from reactions between IS and AS (see Section C). Often, the amount of IS adsorbed depends on the partial pressure of IS in the gas phase and on the strength of adsorption. As a result, the IS may sometimes be stripped from the catalyst by passage of inert gas at a moderate temperature. If a chemical bond has formed between IS and AS, chemical treatment may also remove IS. The most common example of this is the removal of sulfur from the surface by passage of hydrogen. 

Catalyst poisoning results from screening of the surface of the catalyst The molecule of poison does not permit the reacting substances to come into contact with the catalyst. Since the radius of chemical forces is small, the action of the catalyst cannot be manifested. The well-known studies of Maxtod 24) may serve as an illustration to this statement. As Garner 25) has pointed out, Maxted s results can be explained by the multiple theory. 

Studies of current-voltage curves have shown that the electrocatalytic reduction mechanism of isolated ethylenic bonds proceeds mainly by adsorbed H2. The introduction of catalyst poison results in inhibition... 

The combined result of two such determinations yielded a leak size figure of 8.8% of the feed flow (with a relative standard deviation of less than 5%). This figure could sufficiently explain the product quality problems experienced, whose alternative explanation in turn was catalyst poisoning. 

Alkali AletalIodides. Potassium iodide [7681-11-0] KI, mol wt 166.02, mp 686°C, 76.45% I, forms colorless cubic crystals, which are soluble in water, ethanol, methanol, and acetone. KI is used in animal feeds, catalysts, photographic chemicals, for sanitation, and for radiation treatment of radiation poisoning resulting from nuclear accidents. Potassium iodide is prepared by reaction of potassium hydroxide and iodine, from HI and KHCO, or by electrolytic processes (107,108). The product is purified by crystallization from water (see also Feeds and feed additives Photography). 

Catalysts commonly lose activity in operation as a result of accumulation of materials from the reactant stream. Catalyst poisoning is a chemical phenomenon, A catalyst poison is a component such as a feed impurity that as a result of chemisorption, even in smaH amounts, causes the catalyst to lose a substantial fraction of its activity. For example, sulfur compounds in trace amounts poison metal catalysts. Arsenic and phosphoms compounds are also poisons for a number of catalysts. Sometimes the catalyst surface has such a strong affinity for a poison that it scavenges it with a high efficiency. The... 

The results from Figures 6 and 7 support the observation that acetic acid combustion is accelerated by the presence of Au and KOAc. The evolution of carbon dioxide is enhanced by both Au and KOAc, while the evolution of carbon monoxide is enhanced by the presence of KOAc and suppressed by the presence of Au. This shows that acetic acid combustion is more complete with a Pd-Au loy versus Pd alone which is important since carbon monoxide can act as a tempor catalyst poison in the process. These results agree with Nakamura and Yasui s (1980) on acetic acid oxidation which showed an increase in acetic acid combustion when KOAc is added to a Pd catalyst. 

So far, certain biomimetic catalysts (1 and 2b in Fig. 18.17) have been shown to reduce O2 to H2O under a slow electron flux at physiologically relevant conditions (pH 7,0.2-0.05 V potential vs. NHE) and retain their catalytic activity for >10" turnovers. Probably, only the increased stability of the turning-over catalyst is of relevance to the development of practical ORR catalysts for fuel cells. In addition, biomimetic catalysts of series 1,2,3, and 5, and catalyst 4b are the only metalloporphyrins studied in ORR catalysis with well-defined proximal and distal environments. For series 2, which is by far the most thoroughly studied series of biomimetic ORR catalysts, these well-defined environments result in an effective catalysis that seems to be the least sensitive among all metalloporphyrins to the electrode material (whether the catalyst is adsorbed or in the film) and to chemicals present in the electrolyte or in the O2 stream, including typical catalyst poisons (CO and CN ). 

We have studied the hydrogenolysis of 2-(perfluorohexyl)ethane thiocyanate to 2-(perfluorohexyl)ethane thiol. It was discovered that perfluoroalkyl thiocyanates can be reduced to thiols and co-product hydrogen cyanide with molecular hydrogen in the presence of a carbon-supported palladium-tin catalyst. This result is surprising since it is known that palladium and other gronps 8 to 10 metal catalysts are poisoned by the product thiol, traces of hydrogen snlfide byprodnct, and the hydrogen cyanide co-product. For that reason, we characterized the catalyst to understand why it was so robust under conditions that would normally poison snch a catalyst. 

As an example, consider the use of PVPy as a solid poison in the study of poly(noibomene)-supported Pd-NHC complexes in Suzuki reactions of aryl chlorides and phenylboroiuc acid in DMF (23). This polymeric piecatalyst is soluble under some of the reaction conditions employed and thus it presents a different situation from the work using porous, insoluble oxide catalysts (12-13). Like past studies, addition of PVPy resulted in a reduction in reaction yield. However, the reaction solution was observed to become noticeably more viscous, and the cause of the reduced yield - catalyst poisoning vs. transport limitations on reaction kinetics - was not immediately obvious. The authors thus added a non-functionalized poly(styrene), which should only affect the reaction via non-specific physical means (e.g., increase in solution viscosity, etc.), and also observed a decrease in reaction yield. They thus demonstrated a drawback in the use of the potentially swellable PVPy with soluble (23) or swellable (20) catalysts in certain solvents. 

Researchers at Merck Co. [35] who, together with scientists from Solvias, had developed the enantioselective hydrogenation of unprotected enamine amides and esters [36], reported a more recent example of product inhibition. The product amine amide or ester was found to be an inhibitor of the catalyst, and indeed instances of catalyst poisoning by amines have been reported several times (see later). The authors also found an excellent solution to this problem the addition of BOC-anhydride to the hydrogenation reaction neatly reacts away all the amine to form the BOC-protected amine, whereas the enamine was left unreacted (Scheme 44.4). This addition resulted in a remarkable rate enhancement [35]. 

Steam Stability. Steam stability of SOx removal agents is strongly affected by temperature. We have seen previously that at 1350 F deactivation of cerium/alumina additive, caused by silica poisoning, was influenced by how long the additive was steamed and whether the additive was steamed in the presence or absence of cracking catalyst. These results were extended to other temperatures. 

Fig. 12.4. Stationary-state solutions and limit cycles for surface reaction model in presence of catalyst poison K3 = 9, k2 = 1, k3 = 0.018. There is a Hopf bifurcation on the lowest branch p = 0.0237. The resulting stable limit cycle grows as the dimensionless partial pressure increases and forms a homoclinic orbit when p = 0.0247 (see inset). The saddle-node bifurcation point is at...

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