Catalysis deactivation

H. Berger (Koninklijke/Shell Laboratorium, Amsterdam) Concerning the effect of cyanides on metal catalysis (deactivation and formation of oxygenated products), what are your arguments against the explanation that the metal ion becomes completely inactive, while the products arise from a mechanism analogous to that proposed by Berger [Rec. Trav. Chim. 82, 733 (1963)] for the oxidation in tert-butyl alcohol with excess mercaptan relative to base, Did you check that no hydrolysis of disulfide occurs in the presence of cyanide ... 

C,H. Bartholomew and J.B. Butt (Ekiitora), Catalysi Deactivation 1B91 1991 El evier Science Publishers B.V., Amsterdam... 

The components in catalysts called promoters lack significant catalytic activity tliemselves, but tliey improve a catalyst by making it more active, selective, or stable. A chemical promoter is used in minute amounts (e.g., parts per million) and affects tlie chemistry of tlie catalysis by influencing or being part of tlie catalytic sites. A textural (structural) promoter, on tlie otlier hand, is used in massive amounts and usually plays a role such as stabilization of tlie catalyst, for instance, by reducing tlie tendency of tlie porous material to collapse or sinter and lose internal surface area, which is a mechanism of deactivation. 

C, 0.356—1.069 m H2/L (2000—6000 fU/bbl) of Hquid feed, and a space velocity (wt feed per wt catalyst) of 1—5 h. Operation of reformers at low pressure, high temperature, and low hydrogen recycle rates favors the kinetics and the thermodynamics for aromatics production and reduces operating costs. However, all three of these factors, which tend to increase coking, increase the deactivation rate of the catalyst therefore, operating conditions are a compromise. More detailed treatment of the catalysis and chemistry of catalytic reforming is available (33—35). Typical reformate compositions are shown in Table 6. 

Metal Deactivators. The abiUty of metal ions to catalyse oxidation can be inhibited by metal deactivators (19). These additives chelate metal ions and increase the potential difference between the oxidised and reduced states of the metal ions. This decreases the abiUty of the metal to produce radicals from hydroperoxides by oxidation and reduction (eqs. 15 and 16). Complexation of the metal by the metal deactivator also blocks its abiUty to associate with a hydroperoxide, a requirement for catalysis (20). 

The typical industrial catalyst has both microscopic and macroscopic regions with different compositions and stmctures the surfaces of industrial catalysts are much more complex than those of the single crystals of metal investigated in ultrahigh vacuum experiments. Because surfaces of industrial catalysts are very difficult to characterize precisely and catalytic properties are sensitive to small stmctural details, it is usually not possible to identify the specific combinations of atoms on a surface, called catalytic sites or active sites, that are responsible for catalysis. Experiments with catalyst poisons, substances that bond strongly with catalyst surfaces and deactivate them, have shown that the catalytic sites are usually a small fraction of the catalyst surface. Most models of catalytic sites rest on rather shaky foundations. 

Monooximes of a-diketones have found applicability in the synthesis of 2-aminopyrazine 1-oxides by condensation with a-aminonitriles, and this reaction was used by White and coworkers in an approach to the synthesis of Cypridina etioluciferamine (Scheme 66 R = 3-indoloyl) (73T3761). In this instance, the use of TiCU as a catalyst was essential, since the carbonyl group in 3-acylindoles is normally deactivated and the required amine/carbonyl condensation is impractically slow. Under normal circumstances the carbonyl group in simple alkyl-substituted monoximes of a-diketones is the more reactive site and the reaction is rapid, requiring no catalysis (69LA(726)loo). 

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

Volume 34 Catalyst Deactivation 1987. Proceedings of the 4th International Symposium, Antwerp, September 29-October 1,1987 edited by B. Delmon and G.F. Froment Volume 35 Keynotes in Energy-Related Catalysis edited by S. Kaliaguine... 

Traces of bases such as methylimidazole in the final ionic liquid product can play an unfavorable role in some common applications of ionic liquids (such as bipha-sic catalysis). Many electrophilic catalyst complexes will coordinate the base in an irreversible manner and be deactivated. 

Bromine sulphate BrHS04 has been proposed as a possible molecular bro-minating species, since the catalysis by sulphuric acid of the bromination of benzoic acid by hypobromous acid was much greater than by perchloric acid of the same acidity198. Its reactivity was considerably less than that of H2OBr+ so that an enhanced rate spread is observed and its reactions only become noticeable with the least deactivated (i.e. most reactive) compounds employed in this particular study. 

Cyclodiphosphazanes(III) 27 shown in Scheme 16 undergo oxidation reactions to give the cyclodiphosphazanes(V) of type 28. These are prospective ligands in catalysis since these ligands due to lack of phosphorus lone-pairs are less susceptible to the destructive cycloreversion of the ligands. Hence they could prevent catalyst deactivation in the process. When treated with trimethyl aluminum the cyclodiphosphazanes form symmetrically substituted bimetallic species of type 29 [90]. Characterization by single-crystal X-ray studies show... 

A general frustration in the field of catalysis is the occurrence of deactivation. 

Proceedings of the Third World Congress on Oxidation Catalysis, San Diego, CA, U.S.A., 21-26 September 1997 edited by R.K. Grasselli,S.T.Oyama, A.M. Gaffney and J.E. Lyons Volume 111 Catalyst Deactivation 1997. 

Zeolites have led to a new phenomenon in heterogeneous catalysis, shape selectivity. It has two aspects (a) formation of an otherwise possible product is blocked because it cannot fit into the pores, and (b) formation of the product is blocked not by (a) but because the transition state in the bimolecular process leading to it cannot fit into the pores. For example, (a) is involved in zeolite catalyzed reactions which favor a para-disubstituted benzene over the ortho and meso. The low rate of deactivation observed in some reactions of hydrocarbons on some zeoUtes has been ascribed to (b) inhibition of bimolecular steps forming coke. 

When dicarbene complexes of the form 21 were tested for 1-bntene or propene dimerisation, npon activation with AfEt Cl or MAO in tolnene, rapid deactivation took place yielding Ni(0) [25]. It was shown that this decomposition did indeed involve carbene-hydride and carbene-aUcyl rednctive elimination. Some dimerisation was evident at -15°C (TON = 50), however decomposition of the intermediate Ni species seemed too rapid for effective catalysis. In contrast, when the complexes were... 

According to the classical definition of catalysis a catalyst does not cheinge during reaction. In practice this is not true during operation the catalyst loses activity, and often also selectivity and mechanical strength. Catalyst deactivation is a common phenomenon rather than exception. 

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