Spherical catalyst

Matsumoto generated group 4 metal catalysts by cosupporting bis(cyclopentadienyl)-, mono(cyclopen-tadienyl)-, or cyclopentadienyl-free compounds with ferricinium or dimethylanilinium tetrakis(pentafluo-rophenylborate) on a variety of carriers. Triisobutyl-aluminum can be added in the support step or added to the reactor with the catalyst. Spherical particles with bulk densities as high as 0.36 g/cm are formed using this technique. 

Example 3.6.1 Luss and Amundson [33] give the following data for the combustion of coke in a typical cracking catalyst. Predict the maximum temperature rise in the pellet during the combustion. Consider the catalyst spherical. 

Apart from this simple result, comparison of stability predictions for the two limiting situations can be made only by direct numerical computation, and for this purpose a specific algebraic form must be assumed for the reaction rate function, and a specific shape for che catalyst pellet. In particular, Lee and Luss considered a spherical pellet and a first order... 

Rounded materials such as catalyst and round sand have sphericities on the order of 0.9 or higher. Examples of sphericity of various powders are shown in Table 1. 

A weU-known feature of olefin polymerisation with Ziegler-Natta catalysts is the repHcation phenomenon ia which the growing polymer particle mimics the shape of the catalyst (101). This phenomenon allows morphological control of the polymer particle, particularly sise, shape, sise distribution, and compactness, which greatiy influences the polymerisation processes (102). In one example, the polymer particle has the same spherical shape as the catalyst particle, but with a diameter approximately 40 times larger (96). 

The catalyst combines two essential ingredients found in eadier catalysts, vanadium oxide and titanium dioxide, which are coated on an inert, nonporous carrier in a layer 0.02- to 2.0-mm thick (13,16). Other elements such as phosphoms are also used. Ring-shaped supports are used instead of spherical supports to give longer catalyst life, less pressure drop though the reactor, and higher yields (17,18). Half rings are even better and allow more catalyst to be loaded (18). 

C and 5 kg/cm pressure (see Molecularsieves). Selectivity for toluene and xylenes peaks at 550°C but continues with increasing temperature for hensene. The Cyclar process (Fig. 6) developed joindy by BP and UOP uses a spherical, proprietary seoHte catalyst with a nonnoble metallic promoter to convert C or C paraffins to aromatics. The drawback to the process economics is the production of fuel gas, alow value by-product. BP operated a... 

Reactants must diffuse through the network of pores of a catalyst particle to reach the internal area, and the products must diffuse back. The optimum porosity of a catalyst particle is deterrnined by tradeoffs making the pores smaller increases the surface area and thereby increases the activity of the catalyst, but this gain is offset by the increased resistance to transport in the smaller pores increasing the pore volume to create larger pores for faster transport is compensated by a loss of physical strength. A simple quantitative development (46—48) follows for a first-order, isothermal, irreversible catalytic reaction in a spherical, porous catalyst particle. 

To add surface area, the supports are uniformly coated with a slurry of gamma-alumina and recalcined under moderate conditions. The wash coat acts to accept the active metals, typically low levels of platinum and palladium, in a conventional impregnation process. In the United States in passenger car apphcations the spherical catalyst is used almost exclusively, and methods have been developed to replace the catalyst without removing the converter shell when vehicle inspection reveals that emission standards are not met. 

The oxychlorination reaction is very exothermic and the catalyst is very active, which makes it necessary to mix the catalyst with an inert diluent to avoid overheating in a fixed-bed reactor. A low surface area, spherically- or ring-shaped alumina or chemical porcelain body can be used as a diluent with the ring-shaped catalyst. The density of the inert material should be similar to the catalyst to avoid segregation during loading, and the size should be slightly different to allow separation of the inert material from the spent catalyst. 

The catalysts used in this CCR commercial service must meet several stringent physical property requirements. A spherical particle is required so that the catalyst flows in a moving bed down through the process reactors and regenerator vessel. These spheres must be able to withstand the physical abuse of being educated and transferred by gas flow at high velocity. The catalyst particles must also have the proper physical properties, such as particle size, porosity, and poresize distribution, to achieve adequate coke combustion kinetics. 

Use of the peUetted converter, developed and used by General Motors starting in 1975, has declined since 1980. The advantage of the peUetted converter, which consists of a packed bed of small spherical beads about 3 mm in diameter, is that the pellets were less cosdy to manufacture than the monolithic honeycomb. Disadvantages were the peUetted converter had 2 to 3 times more weight and volume, took longer to heat up, and was more susceptible to attrition and loss of catalyst in use. The monolithic honeycomb can be mounted in any orientation, whereas the peUetted converter had to be downflow. AdditionaUy, the pressure drop of the monolithic honeycomb is one-half to one-quarter that of a similar function peUetted converter. 

Types ofSCT Catalysts. The catalysts used in the SCR were initially formed into spherical shapes that were placed either in fixed-bed reactors for clean gas apphcations or moving-bed reactors where dust was present. The moving-bed reactors added complexity to the design and in some appHcations resulted in unacceptable catalyst abrasion. As of 1993 most SCR catalysts are either supported on a ceramic or metallic honeycomb or are direcdy extmded as a honeycomb (1). A typical honeycomb block has face dimensions of 150 by 150 mm and can be as long as one meter. The number of cells per block varies from 20 by 20 up to 45 by 45 (39). 

Catalysts may be porous pellets, usually cylindrical or spherical in shape, ranging from 0.16 to 1.27 cm (Ma to V2 in) in diameter. Small... 

If we know the contact angle we can work out r quite easily. We assume that the nucleus is a spherical cap of radius r and use standard mathematical formulae for the area of the solid-liquid interface, the area of the catalyst-solid interface and the volume of the nucleus. For 0 0 90° these are ... 

If the nucleus wets the catalyst well, with 6= 10°, say, then eqn. (7.15) tells us that het IS.lrt,. In other words, if we arrange our 10 atoms as a spherical cap on a good catalyst we get a much bigger crystal radius than if we arrange them as a sphere. And, as Fig. 7.4 explains, this means that heterogeneous nucleation always "wins" over... 

Figure 1.6.1 Comparison of asymptotic and exact solutions for a first order, non-isothermal reaction in a spherical catalyst pellet. ...

Diffusion effects can be expected in reactions that are very rapid. A great deal of effort has been made to shorten the diffusion path, which increases the efficiency of the catalysts. Pellets are made with all the active ingredients concentrated on a thin peripheral shell and monoliths are made with very thin washcoats containing the noble metals. In order to convert 90% of the CO from the inlet stream at a residence time of no more than 0.01 sec, one needs a first-order kinetic rate constant of about 230 sec-1. When the catalytic activity is distributed uniformly through a porous pellet of 0.15 cm radius with a diffusion coefficient of 0.01 cm2/sec, one obtains a Thiele modulus y> = 22.7. This would yield an effectiveness factor of 0.132 for a spherical geometry, and an apparent kinetic rate constant of 30.3 sec-1 (106). 

Lapidus (LI) described liquid residence-time distribution studies for air-water and air-hydrocarbon in cocurrent, downward flow through a column of 2-in. diameter and 3-ft height. Spherical glass beads of 3.5. mm diameter and cobalt molybdate catalyst cylinders of -in. diameter were used as packing materials. 

A hydrocarbon is cracked using a silica-alumina catalyst in the form of spherical pellets of mean diameter 2.0 mm. When the reactant concentration is 0.011 kmol/m3, the reaction rate is 8.2 x 10"2 kmol/(m3 catalyst) s. If the reaction is of first-order and the effective diffusivity De is 7.5 x 10 s m2/s, calculate the value of the effectiveness factor r). It may be assumed that the effect of mass transfer resistance in the. fluid external Lo the particles may be neglected. 

Most of the electrochemical promotion studies surveyed in this book have been carried out with active catalyst films deposited on solid electrolytes. These films, typically 1 to 10 pm in thickness, consist of catalyst grains (crystallites) typically 0.1 to 1 pm in diameter. Even a diameter of 0.1 pm corresponds to many (-300) atom diameters, assuming an atomic diameter of 3-10 10 m. This means that the active phase dispersion, Dc, as already discussed in Chapter 11, which expresses the fraction of the active phase atoms which are on the surface, and which for spherical particles can be approximated by ... 

Example 10.6 A commercial process for the dehydrogenation of ethylbenzene uses 3-mm spherical catalyst particles. The rate constant is 15s , and the diffusivity of ethylbenzene in steam is 4x 10 m /s under reaction conditions. Assume that the pore diameter is large enough that this bulk diffusivity applies. Determine a likely lower bound for the isothermal effectiveness factor. 

Determine the position of the reaction front in the diffusion-limited decoking of a spherical cracking catalyst. 

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