Catalyst deposits

By passing the alcohol vapour over a copper - chromium oxide catalyst deposit on pumice and heated to 330°, for example ... 

By dropping au aromatic acid either alone or mixed with an aliphatic acid into a tube containing a thoria catalyst deposited on pumice and heated to 400-450°. This method is generally employed for the preparation of mixed aromatic - aliphatic ketones. Excess of the aUphatic acid is usually present since this leads to by-products which are easily separated and also tends to increase the yield of the desired ketone at the expense of the symmetrical ketone of the aromatic acid. Thus —... 

D. H. Linden, "Catalyst Deposition in FCCU Power Recovery Systems," presented at Katalistiks 7thA.nnualFCC Symposium, Venice, Italy, May 1986. 

Usually they are employed as porous pellets in a packed bed. Some exceptions are platinum for the oxidation of ammonia, which is in the form of several layers of fine-mesh wire gauze, and catalysts deposited on membranes. Pore surfaces can be several hundred mVg and pore diameters of the order of 100 A. The entire structure may be or catalytic material (silica or alumina, for instance, sometimes exert catalytic properties) or an active ingredient may be deposited on a porous refractory carrier as a thin film. In such cases the mass of expensive catalytic material, such as Pt or Pd, may be only a fraction of 1 percent. 

When a carrier is impregnated with a solution, where the catalyst deposits will depend on the rate of diffusion and the rate of adsorption on the carrier. Many studies have been made of Pt deposition from chloroplatinic acid (HgPtClg) with a variety of acids and salts as coim-pregnants. HCl results in uniform deposition of Pt. Citric or oxalic acid drive the Pt to the interior. HF coimpregnant produces an egg white profile. Photographs show such varied distributions in a single pellet. 

At that time it was first reported that the catalytic activity and selectivity of conductive catalysts deposited on solid electrolytes can be altered in a very pronounced, reversible and, to some extent, predictable manner by applying electrical currents or potentials (typically up to 2 V) between the catalyst and a second electronic conductor (counter electrode) also deposited... 

Figure 2.3. Catalysis (0), classical promotion ( ), electrochemical promotion ( , ) and electrochemical promotion of a classically promoted (sodium doped) ( , ) Rh catalyst deposited on YSZ during NO reduction by CO in presence of gaseous 02.14 The Figure shows the temperature dependence of the catalytic rates and turnover frequencies of C02 (a) and N2 (b) formation under open-circuit (o.c.) conditions and upon application (via a potentiostat) of catalyst potential values, UWr, of+1 and -IV. Reprinted with permission from Elsevier Science.

Figure 4.50. Transient effect of constant applied current (I=+300 pA) on the rate of C2H4 oxidation on Ir02 and on 75mol% Ir02 - 25%Ti02 and 25% Ir02 - 75%Ti02 composite catalysts deposited on YSZ. Note the decrease in p upon increasing the Ti02 content and the appearance of permanent NEMCA in all cases.124...

Figure 12.1, Principle of electrochemical promotion of a finely dispersed catalyst deposited on an electronically conductive material.7,li 15...

On the other hand, as already discussed in Chapter 11 in connection to the effect of metal-support interactions, it appears that a fully dispersed noble metal catalyst on porous YSZ is already at a NEMCA or electroche-mically-promoted state, i.e. it is covered by an effective double layer of promoting backspillover O2 ions. This can explain both the extreme catalytic activity ofZr02- and Ti02- supported commercial catalysts, as well as the difficulty so far to induce NEMCA on fully dispersed noble metal catalysts deposited on YSZ. 

Do all catalytic reactions on conducting catalysts deposited on solid electrolytes exhibit electrochemical promotion (NEMCA) behaviour ... 

Photoreduction of Si02 doped by six valance molybdenum results in decrease of the surface concentration of Mo ions and, as a consequence, reduces the capability of the sample to emit 2. However, such a treatment does not lead to a complete suppression of emission capability because, according to [96], illumination reduces only 30% of Mo ions in molybdenum oxide catalysts deposited on Si02. 

Table 8.9. NO dissociation over reduced rare-earth oxides and over 1% Pt catalysts deposited on these oxides. Gas Prior to NO dissociation (970 ppm NO), the samples are reduced for 1 h in H2 at 500°C [86]...

Cross-flow filtration systems utilize high liquid axial velocities to generate shear at the liquid-membrane interface. Shear is necessary to maintain acceptable permeate fluxes, especially with concentrated catalyst slurries. The degree of catalyst deposition on the filter membrane or membrane fouling is a function of the shear stress at the surface and particle convection with the permeate flow.16 Membrane surface fouling also depends on many application-specific variables, such as particle size in the retentate, viscosity of the permeate, axial velocity, and the transmembrane pressure. All of these variables can influence the degree of deposition of particles within the filter membrane, and thus decrease the effective pore size of the membrane. 

Steam reforming is a heterogeneously catalyzed process, with nickel catalyst deposited throughout a preformed porous support. It is empirically observed in the industry, that conversion is proportional to the geometric surface area of the catalyst particles, rather than the internal pore area. This suggests that the particle behaves as an egg-shell type, as if all the catalytic activity were confined to a thin layer at the external surface. It has been demonstrated by conventional reaction-diffusion particle modelling that this behaviour is due to... 

Wacker (1) A general process for oxidizing aliphatic hydrocarbons to aldehydes or ketones by the use of oxygen, catalyzed by an aqueous solution of mixed palladium and copper chlorides. Ethylene is thus oxidized to acetaldehyde. If the reaction is conducted in acetic acid, the product is vinyl acetate. The process can be operated with the catalyst in solution, or with the catalyst deposited on a support such as activated caibon. There has been a considerable amount of fundamental research on the reaction mechanism, which is believed to proceed by alternate oxidation and reduction of the palladium ... 

Fig. 13.11 Process path to fabricate the triode emitter structure, showing layer growth, etching, catalyst deposition, and CNT growth steps.

The inner cavity of carbon nanotubes stimulated some research on utilization of the so-called confinement effect [33]. It was observed that catalyst particles selectively deposited inside or outside of the CNT host (Fig. 15.7) in some cases provide different catalytic properties. Explanations range from an electronic origin due to the partial sp3 character of basal plane carbon atoms, which results in a higher n-electron density on the outer than on the inner CNT surface (Fig. 15.4(b)) [34], to an increased pressure of the reactants in nanosized pores [35]. Exemplarily for inside CNT deposited catalyst particles, Bao et al. observed a superior performance of Rh/Mn/Li/Fe nanoparticles in the ethanol production from syngas [36], whereas the opposite trend was found for an Ru catalyst in ammonia decomposition [37]. Considering the substantial volume shrinkage and expansion, respectively, in these two reactions, such results may indeed indicate an increased pressure as the key factor for catalytic performance. However, the activity of a Ru catalyst deposited on the outside wall of CNTs is also more active in the synthesis of ammonia, which in this case is explained by electronic properties [34]. 

Direct metal deposition from metallic sources has been extensively used for model catalyst deposition for high-throughput and combinatorial studies. However, these methods are also increasingly used to deposit practical electrocatalyst materials. The best known approach is the one developed by 3M researchers have used physical vapor deposition to deposit Pt and Ft alloys onto nanostructured (NS) films composed of perylene red whiskers. The approach has been recently been reviewed by Debe. ... 

Dehydrogenation of cyclohexane (1) Pt catalyst deposited within the pores of the membrane (Pt 34 wt.%) (2) Pt/Vycor glass pellets packed on tube side (Pt 34wt.%). 

Dehydrogenation of cyclohexane. Pd catalyst deposited within the pores of the membrane. 

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