Platinum catalyst poison with

Hydrosilylation. Historically, the synthesis of the silyl chloride intermediate from DAM and TCS requires between 100-200 ppm of platinum. Often, the hydrosilylation would terminate prior to completion, with yields as low as 40%. To determine whether DAM was responsible for poor reaction results, the diallyl fumarate (DAF) isomer was evaluated as an alternate substrate DAF is a weaker inhibitor of platinum The comparison revealed that when the DAF and DAM were distilled prior to use, there were no significant differences in reaction kinetics. It was determined that a sulfur contaminant found in commercial sources of DAM - assumed to be a residual of acid catalyst from the maleate esterification - results in poisoning of the platinum catalyst. Thus with distillation, DAM can now be hydrosilylated with TCS in the presence of only 10 ppm platinum catalyst. This observation was consistently reproduced when utilizing an active platinum catalyst complex. Consequently, the hydrosilylation offers > 99% yield with respect to depletion of either DAF or DAM, and severe coloration is completely eliminated from the final product by reduction of the amount of platinum catalyst required. 

R SiH and CH2= CHR interact with both PtL and PtL 1. Complexing or chelating ligands such as phosphines and sulfur complexes are exceUent inhibitors, but often form such stable complexes that they act as poisons and prevent cute even at elevated temperatures. Unsaturated organic compounds are preferred, such as acetylenic alcohols, acetylene dicarboxylates, maleates, fumarates, eneynes, and azo compounds (178—189). An alternative concept has been the encapsulation of the platinum catalysts with either cyclodextrin or in thermoplastics or siUcones (190—192). 

Catalytic Oxidation. Catalytic oxidation is used only for gaseous streams because combustion reactions take place on the surface of the catalyst which otherwise would be covered by soHd material. Common catalysts are palladium [7440-05-3] and platinum [7440-06-4]. Because of the catalytic boost, operating temperatures and residence times are much lower which reduce operating costs. Catalysts in any treatment system are susceptible to poisoning (masking of or interference with the active sites). Catalysts can be poisoned or deactivated by sulfur, bismuth [7440-69-9] phosphoms [7723-14-0] arsenic, antimony, mercury, lead, zinc, tin [7440-31-5] or halogens (notably chlorine) platinum catalysts can tolerate sulfur compounds, but can be poisoned by chlorine. 

The precious-metal platinum catalysts were primarily developed in the 1960s for operation at temperatures between about 200 and 300°C (1,38,44). However, because of sensitivity to poisons, these catalysts are unsuitable for many combustion apphcations. Variations in sulfur levels of as Httle as 0.4 ppm can shift the catalyst required temperature window completely out of a system s operating temperature range (44). Additionally, operation withHquid fuels is further compHcated by the potential for deposition of ammonium sulfate salts within the pores of the catalyst (44). These low temperature catalysts exhibit NO conversion that rises with increasing temperature, then rapidly drops off, as oxidation of ammonia to nitrogen oxides begins to dominate the reaction (see Fig. 7). 

A sophisticated quantitative analysis of experimental data was performed by Voltz et al. (96). Their experiment was performed over commercially available platinum catalysts on pellets and monoliths, with temperatures and gaseous compositions simulating exhaust gases. They found that carbon monoxide, propylene, and nitric oxide all exhibit strong poisoning effects on all kinetic rates. Their data can be fitted by equations of the form ... 

The catalytic system used in the Pacol process is either platinum or platinum/ rhenium-doped aluminum oxide which is partially poisoned with tin or sulfur and alkalinized with an alkali base. The latter modification of the catalyst system hinders the formation of large quantities of diolefins and aromatics. The activities of the UOP in the area of catalyst development led to the documentation of 29 patents between 1970 and 1987 (Table 6). Contact DeH-5, used between 1970 and 1982, already produced good results. The reaction product consisted of about 90% /z-monoolefins. On account of the not inconsiderable content of byproducts (4% diolefins and 3% aromatics) and the relatively short lifetime, the economics of the contact had to be improved. Each diolefin molecule binds in the alkylation two benzene molecules to form di-phenylalkanes or rearranges with the benzene to indane and tetralin derivatives the aromatics, formed during the dehydrogenation, also rearrange to form undesirable byproducts. 

On the surface of metal electrodes, one also hnds almost always some kind or other of adsorbed oxygen or phase oxide layer produced by interaction with the surrounding air (air-oxidized electrodes). The adsorption of foreign matter on an electrode surface as a rule leads to a lower catalytic activity. In some cases this effect may be very pronounced. For instance, the adsorption of mercury ions, arsenic compounds, or carbon monoxide on platinum electrodes leads to a strong decrease (and sometimes total suppression) of their catalytic activity toward many reactions. These substances then are spoken of as catalyst poisons. The reasons for retardation of a reaction by such poisons most often reside in an adsorptive displacement of the reaction components from the electrode surface by adsorption of the foreign species. 

In technical hydrocarbon reforming processes using platinum catalysts, high hydrogen pressures are usually used to inhibit catalyst poisoning and coke formation as far as possible, for instance a total pressure of several atmospheres to several tens of atmospheres, with a several-fold excess of hydrogen in the reactant mixture. 

Nitric acid synthesis, platinum-group metal catalysts in, 19 621 Nitric acid wet spinning process, 11 189 Nitric oxide (NO), 13 791-792. See also Nitrogen oxides (NOJ affinity for ruthenium, 19 638—639 air pollutant, 1 789, 796 cardioprotection role, 5 188 catalyst poison, 5 257t chemistry of, 13 443—444 control of, 26 691—692 effect on ozone depletion, 17 785 mechanism of action in muscle cells, 5 109, 112-113 oxidation of, 17 181 in photochemical smog, 1 789, 790 reduction with catalytic aerogels, l 763t, 764... 

Catalyst poisoning. The more or less permanent deactivation of a catalyst by chemical reaction with a contaminant. Sulfur will poison platinum catalysts vanadium will poison zeolyte catalysts. 

Alkynes may also be hydrogenated, initially to alkenes, and then further to alkanes. By suitable modification of the catalyst, it has proved possible to stop the reaction at the intermediate alkene. Typically, platinum or palladium catalysts partially deactivated (poisoned) with lead salts are fonnd to be suitable for reduction of alkynes to alkenes. Again, syn addition is observed. 

An even more remarkable fact is that catalysts may be poisoned with respect to one reaction while retaining their activity with respect to other reactions. Vavon and Huson found that the hydrogenation of propyl ketone in presence of colloidal platinum was inhibited by amounts of carbon disulphide insufficient to prevent the hydrogenation of piperonal and nitrobenzene. Further amounts of carbon disulphide stopped the hydrogenation of piperonal but not that of nitrobenzene. 

---