Catalytic particle

Figure 2.2.4 (Berty 1983) shows a tubular reactor that has a thermosiphon temperature control system. The reaction is conducted in the vertical stainless steel tube that can have various diameters, 1/2 in. being the preferred size. If used for fixed bed catalytic studies, it can be charged with a single string of catalytic particles just a bit smaller than the tube, e.g., 5/16 particles in a l/2 O.D. tube. With a smaller catalyst, a tube with an inside diameter of up to three to four particle diameters can be used. With such catalyst charges and a reasonably high Reynolds number— above 500, based on particle diameter—this reactor...

Fig. 2. Vapour-grown carbon fiber. showing relatively early stage of growth at the tip the seeded Fe catalytic particle is encapsulated.

As in the case of graphite-supported catalysts, some metal particles were also encapsulated by the deposited carbon (Fig. 4). However, the amount of encapsulated metal was much less. Differences in the nature of encapsulation were observed. Almost all encapsulated metal particles on silica-supported catalysts were found inside the tubules (Fig. 4(a)). The probable mechanism of this encapsulation was precisely described elsewhere[21 ]. We supposed that they were catalytic particles that became inactive after introduction into the tubules during the growth process. On the other hand, the formation of graphite layers around the metal in the case of graphite-supported catalysts can be explained on the basis of... 

Fig. 4. Catalytic particles encapsulated in tubules on Co-Si02 (a) low magnification (b) HREM.

Fig. 5. Reactant concentration with catalytic particle size.

In a slurry reactor (Fig 5.4.74), the catalyst is present as finely divided particles, typically in the range 1-200 pm. A mechanical stirrer, or the gas flow itself, provides the agitation power required to keep the catalytic particles in suspension. One advantage is the high catalyst utilization not only is the diffusion distance short, it is al.so possible to obtain high mass-transfer rates by proper mixing. 

Inspection of Fig. 15.3 reveals that while for jo 0.1 nAcm , the effectiveness factor is expected to be close to 1, for a faster reaction with Jo 1 p,A cm , it will drop to about 0.2. This is the case of internal diffusion limitation, well known in heterogeneous catalysis, when the reagent concentration at the outer surface of the catalyst grains is equal to its volume concentration, but drops sharply inside the pores of the catalyst. In this context, it should be pointed out that when the pore size is decreased below about 50 nm, the predominant mechanism of mass transport is Knudsen diffusion [Malek and Coppens, 2003], with the diffusion coefficient being less than the Pick diffusion coefficient and dependent on the porosity and pore stmcture. Moreover, the discrete distribution of the catalytic particles in the CL may also affect the measured current owing to overlap of diffusion zones around closely positioned particles [Antoine et ah, 1998]. 

We first consider the stmcture of the rate constant for low catalyst densities and, for simplicity, suppose the A particles are converted irreversibly to B upon collision with C (see Fig. 18a). The catalytic particles are assumed to be spherical with radius a. The chemical rate law takes the form dnA(t)/dt = —kf(t)ncnA(t), where kf(t) is the time-dependent rate coefficient. For long times, kf(t) reduces to the phenomenological forward rate constant, kf. If the dynamics of the A density field may be described by a diffusion equation, we have the well known partially absorbing sink problem considered by Smoluchowski [32]. To determine the rate constant we must solve the diffusion equation... 

This formulation assumes that the continuum diffusion equation is valid up to a distance a > a, which accounts for the presence of a boundary layer in the vicinity of the catalytic particle where the continuum description no longer applies. The rate constant ky characterizes the reactive process in the boundary layer. If it approximated by binary reactive collisions of A with the catalytic sphere, it is given by kqf = pRGc(8nkBT/m)1 2, where pR is the probability of reaction on collision. 

Fig. 29. Snapshots of particle volume fraction fields obtained while solving a kinetic theory-based TFM. 75 pm fluid catalytic particles in ambient air. Simulations were done over a 16 x 32 cm periodic domain. The average particle volume fraction in the domain is 0.05. Dark (light) color indicates regions of high (low) particle volume fractions. (See Refs. Agrawal et al., 2001 Andrews et al., 2005) for other parameter values.) Source Andrews and Sundaresan (2005).

Thermal conductivities of two porous catalytic particles are nickel-tungsten, 0.47 W/(m)0C), platinum-alumina, 0.22 (Satterfield, Heterogeneous Catalysis in Practice, 1980). 

Recent advances have led to the development of microcalorimeters sensitive enough for low-surface-area ( 1 cm2) solids [71]. This instrumentation has already been used in model systems to determine the energetics of bonding of catalytic particles to the support, and also in adsorption and reaction processes [72,73],... 

It can be seen in the plot in Figure 11 that EA . shows a clear temperature dependence. For rising temperatures the mass transport limitation can be observed, which leads to a lowering of EAs by a factor of V2 in the pore diffusion regime down to 0, owing to the shift of the reaction from the interior of the pore system of the catalytic particle to the outer surface. In the final state, the diffusion through the boundary layer becomes the rate-limiting step of the reaction. 

Operation of cells at higher temperatures such as 80°C, as in membrane fuel cells, is not encouraged here because of the corrosion instability of the hardware, manufactured from titanium or titanium alloy. Even without such constraints, however, this high temperature would be unwelcome as the water produced is present as steam - without the conductive bridge of the liquid phase it would be necessary to bond the catalytic particles to the membrane with all the associated problems of technology and cost. 

In a similar design, DArrigo et al. [78] also used porous silicon as the DL in a fuel cell. The porous silicon was deposited by chemical vapor deposition (CVD) on top of a silicon wafer that already had microgrooves machined on it. Then, catalytic particles were deposited on top of fhe porous silicon layer. Unfortunately, no performance-related data indicating whether the cell was acceptable or not were published for fhis design. 

The gas temperature in the catalytic zone is also the temperature of the catalytic particles. 

Analogy between Supported Molecular Clusters and Small Supported Catalytic Particles... 

The first, made by Ichikawa et al. [29], was the evidence that rhodium or iridium cluster carbonyls, when adsorbed on zinc oxide, titania, lanthanum oxides, zirconia or magnesia, could produce quite selectively ethanol by the Fischer-Tropsch synthesis. This was a timely discovery (metallic catalytic particles produced by traditional methods could not reproduce such selectivity) since it came at a period of geopolitical tension after the Kippur war in 1973, which caused the price of crude oil to increase enormously. Therefore, that period was characterized by intense research into selective Fischer-Tropsch catalysis. 

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