Sensitivity oxidation catalysts

Figure 4.18 shows the positive SIMS spectrum of a silica-supported zirconium oxide catalyst precursor, freshly prepared by a condensation reaction between zirconium ethoxide and the hydroxyl groups of the support. Note the simultaneous occurrence of single ions (H", SR, 7.r ) and molecular ions (SiO, SiOH, ZrO, Zr02 ). Also, the isotope pattern of zirconium is clearly visible. Isotopes are important in the identification of peaks, because all peak intensity ratios must agree with the natural abundances. In addition to the peaks expected from zirconia on silica mounted on an indium foil, the spectrum of Fig. 4.18 also contains peaks from Na, K, and Ca. This is typical for SIMS Sensitivities vary over several orders of magnitude and elements such as the alkalis are detected when present in trace amounts. 

The activity of the Au/metal oxide catalysts is extremely sensitive to the method of preparation. The Au/metal oxide catalysts were prepared by the co-precipitating method [1]. During the course of this study, we have determined that the activity and the stability of the catalyst for room temperature CO oxidation were a function of Ph of the solution, temperature of precipitation, aging temperature and time, catalyst wash procedure, and calcination. 

Au/metal oxides are active for low temperature CO oxidation. The activity of the catalysts is very sensitive to catalyst preparation. All the Au/metal oxides tested for room temperature CO oxidation deactivated substantially with time. The deactivation... 

Catalyst cost constitutes 15-20% of the capital cost of an SCR unit therefore, it is essential to operate at temperatures as high as possible to maximize space velocity and thus minimize catalyst volume. At the same time, it is necessary to minimize the rate of oxidation of S02 to S03, which is more temperature sensitive than the SCR reaction. The optimum operating temperature for the SCR process using titanium and vanadium oxide catalysts is about 38CM180oC. Most installations use an economizer bypass to provide flue gas to the reactors at the desired temperature during periods when flue gas temperatures are low, such as low-load operation. 

The flow-cell design was introduced by Stieg and Nieman [166] in 1978 for analytical uses of CL. Burguera and Townshend [167] used the CL emission produced by the oxidation of alkylamines by benzoyl peroxide to determine aliphatic secondary and tertiary amines in chloroform or acetone. They tested various coiled flow cells for monitoring the CL emission produced by the cobalt-catalyzed oxidation of luminol by hydrogen peroxide and the fluorescein-sensitized oxidation of sulfide by sodium hypochlorite [168], Rule and Seitz [169] reported one of the first applications of flow injection analysis (FTA) in the CL detection of peroxide with luminol in the presence of a copper ion catalyst. They... 

As discussed above, the level of sensitivity of most gas-phase oxidation catalysts is high with regard to the reaction temperature. Therefore, any Stage II-screening tool should operate under isothermal conditions for all active materials, and it is a given prerequisite that thermal equilibrium of the reactor and a homogeneous temperature distribution are essential. 

If the gasifier product stream is intended for downstream use as the feedstock for further upgrading such as methanation, methanol or Fischer Tropsch synthesis, very thorough desulphuri-sation is essential since the catalysts in these upgrading processes are highly sensitive to sulphur poisoning. The methanation catalysts normally cannot tolerate more than 0.05 ppm of sulphur in the feedstock. In addition to H2S sulphur values in the gasifier product it may contain COS, CS2, mercaptans and thiophenes. These are normally removed by activated carbon or zinc oxide filters ahead of the sensitive synthesis catalyst beds. 

An ozone-sensitized oxidative conversion of methane to methanol has been reported.54 A double-layered Sr on La203 then M0O3 on a silica catalyst bed exhibited significantly higher yields of formaldehyde from a methane-air mixture than did M0O3 on silica alone.55... 

Raney-nickel catalysts are barely sensitive to catalyst poisoning (as are Pt-activated cathodes), e.g., by iron deposition, but they deteriorate due to loss of active inner surface because of slow recrystallization—which unavoidably leads to surface losses of 50% and more over a period of 2 years. A further loss mechanism is oxidation of the highly dispersed, reactive Raney nickel by reaction with water (Ni + 2H20 — Ni(OH)2 + 02) under depolarized condition, that is, during off times in contact with the hot electrolyte after complete release of the hydrogen stored in the pores by diffusion of the dissolved gas into the electrolyte. 

Fig. 5. Correlation of the Taft reaction parameter for the dehydration of secondary alcohols (see Table 4) on four different oxide catalysts with the heat of adsorption, A//ads> °f water and diethylether, with the sensitivity of the rate to pyridine poisoning 7> [55] and with the value of the deuterium kinetic isotope effect [123] for the same catalysts.

The co-oxidation of indene and thiophenol in benzene proceeds by a three-step cyclic free radical chain reaction. Autocatalysis associated with the hydroperoxide which is the main primary product occurs, but the effect is complicated by other trace components. The reaction is extremely sensitive to catalysts and inhibitors, and its kinetic features are determined by the initiation and termination processes. 

Unfortunately, many of the organometallic trioxorhenium complexes are light or temperature sensitive, rendering them poor catalysts. Of all the organotri-oxorhenium complexes, only Cp Re03 and MTO have been found to be stable enough to perform well as catalysts and especially the latter is well known as an excellent olefin oxidation catalyst. 

Zinc oxide beds are used to safeguard the sulfur-sensitive LTS catalyst against sulfur poisoning from the expected 1 to 2 ppm H2S + COS slippage on the Sulfinol unit. 

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