Metal deposits catalyst

The catalyst is also employed in the form of the finely-divided metal deposited upon activated carbon (usually containing 5 or 10 per cent. Pd) two methods of preparation are described, in one reduction is effected with alkaline formaldehyde solution and in the other with hydrogen ... 

Indium chemicals and electroplated metal deposits ate replacing mercury (qv) in the manufacture of alkaline batteries (qv). Indium, like mercury, functions to reduce outgassing within the battery and promotes the uniform corrosion of the anode and cathode while the battery is under electrical load. Indium inorganic chemicals also find use as catalysts in various chemical processes. 

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). 

An alternate form of catalyst is pellets. The pellets are available in various diameters or extruded forms. The pellets can have an aluminum oxide coating with a noble metal deposited as the catalyst. The beads are placed in a tray or bed and have a depth of anywhere from 6 to 10 inches. The larger the bead (1/4 inch versus 1/8 inch) the less the pressure drop through the catalyst bed. However, the larger the bead, the less surface area is present in the same volume which translates to less destruction efficiency. Higher pressure drop translates into higher horsepower required for the oxidation system. The noble metal monoliths have a relatively low pressure drop and are typically more expensive than the pellets for the same application. 

Base Metal Catalyst - An alternate to a noble metal catalyst is a base metal catalyst. A base metal catalyst can be deposited on a monolithic substrate or is available as a pellet. These pellets are normally extruded and hence are 100% catalyst rather than deposition on a substrate. A benefit of base metal extruded catalyst is that if any poisons are present in the process stream, a deposition of the poisons on the surface of the catalyst occurs. Depending on the type of contaminant, it can frequently be washed away with water. When it is washed, abraded, or atritted, the outer surface is removed and subsequently a new catalyst surface is exposed. Hence, the catalyst can be regenerated. Noble metal catalyst can also be regenerated but the process is more expensive. A noble metal catalyst, depending on the operation, will typically last 30,000 hours. As a rule of thumb, a single shift operation of 40 hours a week, 50 weeks a year results in a total of 2,000 hours per year. Hence, the catalyst might have a 15 year life expectancy. From a cost factor, a typical rule of thumb is that a catalyst might be 10%-15% of the overall capital cost of the equipment. 

The CF and GF represent the coke- and gas-forming tendencies of an E-cat compared to a standard steam-aged catalyst sample at the same conversion. The CF and GF are influenced by the type of fresh catalyst and the level of metals deposited on the E-cat. Both the coke and gas factors can be indicative of the dehydrogenation activity of the metals on the catalyst. The addition of amorphous alumina to the catalyst will tend to increase the nonselective cracking, which forms coke and gas. 

These metals, when deposited on the E-cat catalyst, increase coke and gas-making tendencies of the catalyst. They cause dehydrogenation reactions, which increase hydrogen production and decrease gasoline yields. Vanadium can also destroy the zeolite activity and thus lead to lower conversion. The deleterious effects of these metals also depend on the regenerator temperature the rate of deactivation of a metal-laden catalyst increases as the regenerator temperature increases. 

As discussed in Chapter 2, nickel, vanadium, and sodium are the metal compounds usually present in the FCC feedstock. These metals deposit on the catalyst, thus poisoning the catalyst active sites. Some of the options available to refiners for reducing the effect of metals on catalyst activity are as follows ... 

When studying the electrochemical promotion behaviour of catalytic oxidations on metals deposited on YSZ, one always makes the same observation Positive currents, i.e. O2 supply to the catalyst, cause NEMCA (electrophobic behaviour) only for high 02 to fuel (Pa/Pd) ratios in the gas phase. How can we explain this, at a first glance, counterintuitive but general observation ... 

Recently, it is reported that Xi02 particles with metal deposition on the surface is more active than pure Ti02 for photocatalytic reactions in aqueous solution because the deposited metal provides reduction sites which in turn increase the efficiency of the transport of photogenerated electrons (e ) in the conduction band to the external sjistem, and decrease the recombination with positive hole (h ) in the balance band of Xi02, i.e., less defects acting as the recombination center[l,2,3]. Xhe catalytic converter contains precious metals, mainly platinum less than 1 wt%, partially, Pd, Re, Rh, etc. on cordierite supporter. Xhus, in this study, solutions leached out from wasted catalytic converter of automobile were used for precious metallization source of the catalyst. Xhe XiOa were prepared with two different methods i.e., hydrothermal method and a sol-gel method. Xhe prepared titanium oxide and commercial P-25 catalyst (Deagussa) were metallized with leached solution from wasted catalytic converter or pure H2PtCl6 solution for modification of photocatalysts. Xhey were characterized by UV-DRS, BEX surface area analyzer, and XRD[4]. 

The most important undesired metallic impurities are nickel and vanadium, present in porphyrinic structures that originate from plants and are predominantly found in the heavy residues. In addition, iron may be present due to corrosion in storage tanks. These metals deposit on catalysts and give rise to enhanced carbon deposition (nickel in particular). Vanadium has a deleterious effect on the lattice structure of zeolites used in fluid catalytic cracking. A host of other elements may also be present. Hydrodemetallization is strictly speaking not a catalytic process, because the metallic elements remain in the form of sulfides on the catalyst. Decomposition of the porphyrinic structures is a relatively rapid reaction and as a result it occurs mainly in the front end of the catalyst bed, and at the outside of the catalyst particles. 

In the following review we will focus on two classes of systems dispersed metal particles on oxide supports as used for a large variety of catalytic reactions and a model Ziegler-Natta catalyst for low pressure olefin polymerization. The discussion of the first system will focus on the characterization of the environment of deposited metal atoms. To this end, we will discuss the prospects of metal carbonyls, which may be formed during the reaction of metal deposits with a CO gas phase, as probes for mapping the environment of deposited metal atoms [15-19]. 

Previous kinetic investigations dealing with the NO + H2 reaction over supported noble metal-based catalysts showed different kinetic features according to the nature of the support [29,53-58], Initially, this reaction has been described in the absence of oxygen on Rh deposited on silica and alumina by the following mechanism [29],... 

For the Pd-silk catalyst,2 PdCl2 was deposited on silk and reduced to Pd° moderate enantioselectivities were obtained for the hydrogenation of a C=C bond (66% enantiomeric excess, ee, which is the difference between enantiomers divided by the sum of enantiomers), but the silk support presented two problems it tended to deteriorate with time on stream and it varied from source to source, so enantioselectivities were not reproducible (Scheme 3.2). On the other hand, deterioration was not a problem with the metal-quartz catalysts. 

One way to overcome the problem of chirality existing only at the metal-matrix interface is to encase the metal particle inside the chiral matrix. In that case, all of the metal surface atoms should be close to a chiral center however, this approach has some problems too. For example, access to the metal surface may be inhibited by the encasing matrix. In spite of this, several attempts have produced moderately successful catalysts by creating metal—polymer catalysts. Pd has been deposited on poly-(5)-leucine (Scheme 3.4) and Pd and Pt colloids have been encased in a polysaccharide to produce catalysts that enanti-oselectively hydrogenated prochiral C=C and C=N bonds (Scheme 3.5).7... 

Typically, the Pd species for Heck couplings are homogeneous catalysts, stabilized by air-sensitive ligands. They present economic and environmental problems regarding separation, regeneration and reuse. These difficulties can be diminished with heterogeneous catalysts that are more easily recoverable from the reaction mixture. As mentioned in Sect. 2.6, a catalyst consisting of palladium metal deposited on por-... 

In contrast to a mixture of redox couples that rapidly reach thermodynamic equilibrium because of fast reaction kinetics, e.g., a mixture of Fe2+/Fe3+ and Ce3+/ Ce4+, due to the slow kinetics of the electroless reaction, the two (sometimes more) couples in a standard electroless solution are not in equilibrium. Nonequilibrium systems of the latter kind were known in the past as polyelectrode systems [18, 19]. Electroless solutions are by their nature thermodyamically prone to reaction between the metal ions and reductant, which is facilitated by a heterogeneous catalyst. In properly formulated electroless solutions, metal ions are complexed, a buffer maintains solution pH, and solution stabilizers, which are normally catalytic poisons, are often employed. The latter adsorb on extraneous catalytically active sites, whether particles in solution, or sites on mechanical components of the deposition system/ container, to inhibit deposition reactions. With proper maintenance, electroless solutions may operate for periods of months at elevated temperatures, and exhibit minimal extraneous metal deposition. 

Spiro [27] has derived quantitative expressions for the catalytic effect of electron conducting catalysts on oxidation-reduction reactions in solution in which the catalyst assumes the Emp imposed on it by the interacting redox couples. When both partial reaction polarization curves in the region of Emp exhibit Tafel type kinetics, he determined that the catalytic rate of reaction will be proportional to the concentrations of the two reactants raised to fractional powers in many simple cases, the power is one. On the other hand, if the polarization curve of one of the reactants shows diffusion-controlled kinetics, the catalytic rate of reaction will be proportional to the concentration of that reactant alone. Electroless metal deposition systems, at least those that appear to obey the MPT model, may be considered to be a special case of the general class of heterogeneously catalyzed reactions treated by Spiro. 

V to +0.7 V vs. RHE for a Pd surface. Normally, this is anodic, or positive, with respect to the Em value of the electroless reaction (Fig. 1). Following removal of the oxide species from the catalyst surface, whether deposition subsequently initiates or not depends on the interplay between the kinetics of the parallel metal ion and O2 reduction reactions, and oxidation of the reducing agent. Once an appropriate Em value is reached, metal deposition will occur. 

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