Metals passivity effects

Table II. Antimony Metals Passivation Effects on Charge Rate...

At high metals levels, the coking characteristics of a cracking catalyst can be greatly increased that is, the ratio of contaminant coke to catalytic coke can be quite high. The effect of the contaminant metals on the coke response is affected not only by the level of metals but also by the type of catalyst and the use of a metals passivator. Catalysts, which contain effective metals traps to inhibit the contaminant effects, do produce much less contaminant coke than catalyst without metal traps. 

Another approach used to reduce the harmful effects of heavy metals in petroleum residues is metal passivation. In this process an oil-soluble treating agent containing antimony is used that deposits on the catalyst surface in competition with contaminant metals, thus reducing the catalytic activity of these metals in promoting coke and gas formation. Metal passivation is especially important in fluid catalytic cracking (FCC) processes. Additives that improve FCC processes were found to increase catalyst life and improve the yield and quality of products. ... 

Steels and stainless steels show preferential nucleation of pits at inclusions, most notably sulphide inclusions ". Other sulphur-rich regions in ferrous and nickel-based alloys may also lead to premature failure. It has been shown that accumulation of sulphur on the surface of these materials retards passivity and enhances dissolution of the metal. These effects occur in any solution in which the metal shows an active region and they are also preferential pitting sites in the presence of chloride. A recent notion for... 

Here, the use of inhibitor formulations having a less dramatic effect on TDS (such as certain tannins) may be extremely beneficial. Formulations are available that are based on tannin chemistry and contain blends that act as oxygen scavengers and metal passivators, with additional sludge dispersant and antifoam properties. 

Supramolecular catalysis can involve passive effects such as the confining of two reactive molecules within a cavity and active effects where the catalyst interacts with the substrate via an active site. The active site may be metal-based as in other kinds of homogeneous catalyst based on transition metals or Lewis acids, or my involve interactions such as hydrogen bonding to bring about both polarisation of the reactants and their mutual spatial organisation. 

Case Studies. As shown in Figure 2, metals passivation is utilized effectively with 4Ni+V concentrations less than 6000 ppm. Specific benefits of antimony metals passivation for two refinery FCC units operating at less than 6000 ppm 4Ni+V are discussed below. 

Both the initiation and continuation of the oxidation are materially affected by temperature (oxidation rates are doubled for each 10°C rise in temperature), but may also be catalyzed by the presence of various metals or by light. The termination of the oxidation reaction may result from the exhaustion of the oxygen supply in lubrication systems or from the formation of stable products R + R - R-R) in the oxidation chain reaction. Antioxidant or oxidation inhibitors may function as chain terminating agents by reacting with free radicals to form stable products, by acting as peroxide decomposers, or they may act as metal passivators to prevent catalytic effects. 

Another process of physical protection is the formation of an oxide layer that makes the metal passive. This procedure is used for aluminium. Aluminium is normally anodized in 10 per cent sulphuric acid with steel or copper cathodes until an oxide thickness of 10-100 pm is obtained. As the more superficial part of the oxide layer has a fairly open structure it is possible to deposit metals (cobalt, nickel, etc.) or organic pigments in the pores and seal with boiling water or with an alkaline solution. The colours after metallic deposition are due to interference effects. Chromic and oxalic acids are also used significantly as electrolyte. 

A computer program was developed for electrochemical equilibria calculations and graphical pH-potential diagram presentation of a one-metal/one-nonmetal/water system. The program can be used for temperatures and pressures exceeding the supercritical point of water. The calculations show that hematite (Fe203) is the oxidation product of iron in supercritical water, and the oxidation product of chromium in supercritical water is an ionic species, Cr04 . Passivation effect of chromium is lost in supercritical water. 

Although the transition metal ehaleogenides usually are quite refractory, direct reaction is feasible in many cases. In some cases (e.g., W and Mo), the oxide is volatile, making the surface at least accessible to reaction. In addition, the metals often have high rates of diffusion in the compounds, thus reducing the surface passivation effect of compound formation. This is probably because diffusion jumps are more probable in the presence of elements that can change their charge states. This property can be helpful in conversion of an oxide to a sulfide via H2S or CS2. 

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