Nickel-molybdenum temperature effect

The catalyst was 100 ml of American Cyanamid HDS-3A, a 1/16-inch diameter extrudate of nickel-molybdenum-alumina. It was diluted with inert, granular alpha-alumina to provide a bed depth of 18 inches in the middle section of a 0.96-inch ID vertical reactor with a 5/16-inch OD internal thermocouple well. The catalyst was progressively more dilute toward the top of the bed to minimize exothermic temperature effects, and end sections were packed with alpha-alumina to provide for preheat and cooling zones. 

The effectiveness of catalysts A and B to desulfurize SRN and blend naphtha was investigated and the results are shown in Table 4. Figure 4, which shows the performance of catalyst A, illustrates that it is easier to desulfurize SRN than blend naphtha. The results also confirmed higher HDS performance with blend naphtha than SRN with both catalysts. This could be due to the refractive material in the hydrocracked fraction of the blend naphtha. With blend naphtha and catalyst A the minimum total sulfur ofO.69 ppm was obtained at 320°C, while with SRN the minimum was 0.37 ppm at 300°C. Above these temperatures, the occurrence of H2S-alkene recombination reactions increased the total sulfur. Nickel-molybdenum catalysts are known to reduce recombination reactions by hydrogenating alkenes. Higher temperatures and very active catalysts can cause cracking at the reactor outlet allowing alkenes production[13],... 

The corrosion behaviour of amorphous alloys has received particular attention since the extraordinarily high corrosion resistance of amorphous iron-chromium-metalloid alloys was reported. The majority of amorphous ferrous alloys contain large amounts of metalloids. The corrosion rate of amorphous iron-metalloid alloys decreases with the addition of most second metallic elements such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium and platinum . The addition of chromium is particularly effective. For instance amorphous Fe-8Cr-13P-7C alloy passivates spontaneously even in 2 N HCl at ambient temperature ". (The number denoting the concentration of an alloy element in the amorphous alloy formulae is the atomic percent unless otherwise stated.)... 

Amorphous Fe-3Cr-13P-7C alloys containing 2 at% molybdenum, tungsten or other metallic elements are passivated by anodic polarisation in 1 N HCl at ambient temperature". Chromium addition is also effective in improving the corrosion resistance of amorphous cobalt-metalloid and nickel-metalloid alloys (Fig. 3.67). The combined addition of chromium and molybdenum is further effective. Some amorphous Fe-Cr-Mo-metalloid alloys passivate spontaneously even in 12 N HCl at 60° C. Critical concentrations of chromium and molybdenum necessary for spontaneous passivation of amorphous Fe-Cr-Mo-13P-7C and Fe-Cr-Mo-18C alloys in hydrochloric acids of various concentrations and different temperatures are shown in Fig. 3.68 ... 

To promote the activity and selectivity of Raney nickel catalysts, alloying of the starting Ni-Al alloy with metal was often used. For instance, Montgomery (ref. 4) prepared catalysts by activating ternary alloy powders of Al (58 wt %)-Ni (37-42 wt %) - M (0.5 wt %) where M = Co, Cr, Cu, Fe and Mo. All promoted catalysts tested were more active than the reference catalyst, in hydrogenation of butyronitrile. Molybdenum was the most effective promoter. With Cr or Ti, hydrogenation of isophtalonitrile on Raney nickel occurred at lower optimum temperature than with non activated nickel (ref. 5). It was shown that addition of Ti or Co to Raney nickel suppressed the formation of secondary amine (ref. 6). 

One other area in which the use of molybdenum disulphide may be undesirable for pre-assembly or anti-seize use is when nickel alloys are used in critical applications, especially at high temperatures. Such alloys are extensively used in aviation gas turbine engines, and there have been cases in which serious failures of gas turbines have been attributed to the effect of molybdenum disulphide-based lubricants on high-temperature components Provided these two hazards are kept in mind, molybdenum disulphide dispersions and pastes are of great value as antiseize compounds and as assembly aids. 

Abbattista et al. (26) found that phosphorus addition prevents crystallization of the y-alumina phase and the transformation from y- to a-alumina in the system AI2O3 —AIPO4 (Fig. 23). More precisely, Morterra et al. (77) reported that phosphates do not affect the phase transition from low-temperature spinel alumina (y-alumina) to high-temperature spinel aluminas 8 and 6 phases) but delay the transition of 8 and 9 to a-alumina (corundum). Stanislaus et al 46) also reported that phosphorus significantly improves the thermal stabihty of the y-alumina phase in P/Al catalysts. However, the same authors found that the positive effect of phosphorus seems to be canceled in the presence of molybdenum due to the formation of aluminum molybdate. Thermal treatments of MoP/Al catalysts at temperatures >700°C result in a considerable reduction of SSA and mechanical strength. The presence of phosphorus does not prevent the reaction between the molybdenum oxo-species and alumina since the interaction between molybdates and phosphates is weak. The presence of nickel does not obviously affect the positive effect of phosphorus in terms of thermal stability 46). On the other hand, Hopkins and Meyers 78) reported that the thermal stability of commercial CoMo/Al and NiMo/Al catalysts is improved by the addition of phosphorus. 

Holzheid A., Borisov A., and Palme H. (1994) The effect of oxygen fugacity and temperature on solubilities of nickel, cobalt and molybdenum in silicate melts. Geochim. Cosmochim. Acta 58, 1975-1981. 

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