Surface Thiele modulus

Catalyst Effectiveness. Even at steady-state, isothermal conditions, consideration must be given to the possible loss in catalyst activity resulting from gradients. The loss is usually calculated based on the effectiveness factor, which is the diffusion-limited reaction rate within catalyst pores divided by the reaction rate at catalyst surface conditions (50). The effectiveness factor E, in turn, is related to the Thiele modulus,

first-order rate constant, a the internal surface area, and the effective diffusivity. It is desirable for E to be as close as possible to its maximum value of unity. Various formulas have been developed for E, which are particularly usehil for analyzing reactors that are potentially subject to thermal instabilities, such as hot spots and temperature mnaways (1,48,51). 

The relationship between effectiveness factor p and Thiele modulus < >l may be calculated for several other regular shapes of particles, where again the characteristic dimension of the particle is defined as the ratio of its volume to its surface area. It is found that... 

The solution of this equation is in the form of a Bessel function 32. Again, the characteristic length of the cylinder may be defined as the ratio of its volume to its surface area in this case, L = rcJ2. It may be seen in Figure 10.13 that, when the effectiveness factor rj is plotted against the normalised Thiele modulus, the curve for the cylinder lies between the curves for the slab and the sphere. Furthermore, for these three particles, the effectiveness factor is not critically dependent on shape. 

As it turns out (section 11.3) increasing the thickness, L, of the porous catalyst electrode film is qualitatively similar, in view of Eq. (11.22) with increasing T as they both increase the Thiele modulus 3>P, thus decrease r)P ( (bp1). They both tend to decrease to the coverage of the promoting species on the catalyst surface, thus they both tend to decrease p and A. 

Figure 5.34. Normalized concentration profiles in a porous sphere for different values of the Thiele modulus. Note that if the latter is large, only a small part of the catalyst near the surface contributes to conversion.

In order for diffusional limitations to be negligible, the effectiveness factor must be close to 1, i.e. nearly complete catalyst utilization, which requires that the Thiele modulus is suffieiently small (< ca. 0.5), see Figure 3.32. Therefore, the surface-over-volume ratio must be as large as possible (particle size as small as possible) from a diffusion (and heat-transfer) point of view. There are many different catalyst shapes that have different SA/V ratios for a given size. 

The term in brackets is a dimensionless group that plays a key role in determining the limitations that intraparticle diffusion places on observed reaction rates and the effectiveness with which the catalyst surface area is utilized. We define the Thiele modulus hT as... 

Figure 12.5 contains a series of curves representing the concentration profile in the spherical pellet for different values of the Thiele modulus s. For small values of 0S, (say less than 0.5) the concentration profile is relatively flat and the reactant concentration is reasonably uniform. For large values of (say greater than 5), the reaction is rapid relative to diffusion and the reactant concentration at the center of the catalyst pellet is less than 7% of that at the external surface. Notice that in all cases the concentration gradient approaches zero at the center of the pellet. 

When the Thiele modulus for the unpoisoned pore is small (i.e., the surface is completely available), the hyperbolic tangent terms become equal to their arguments and is given by... 

This relation is plotted as curve Bin Figure 12.11. Smith (66) has shown that the same limiting forms for are observed using the concept of effective dififusivities and spherical catalyst pellets. Curve B indicates that, for fast reactions on catalyst surfaces where the poisoned sites are uniformly distributed over the pore surface, the apparent activity of the catalyst declines much less rapidly than for the case where catalyst effectiveness factors approach unity. Under these circumstances, the catalyst effectiveness factors are considerably less than unity, and the effects of the portion of the poison adsorbed near the closed end of the pore are not as apparent as in the earlier case for small hr. With poisoning, the Thiele modulus hp decreases, and the reaction merely penetrates deeper into the pore. 

This equation indicates that a small amount of poisoned surface can lead to a sharp decline in apparent activity. For example, if only 10% of the catalyst surface has been deactivated in the case where the Thiele modulus for the unpoisoned reaction is 40, 3F = 0.200 so that the... 

For situations where the reaction is very slow relative to diffusion, the effectiveness factor for the poisoned catalyst will be unity, and the apparent activation energy of the reaction will be the true activation energy for the intrinsic chemical reaction. As the temperature increases, however, the reaction rate increases much faster than the diffusion rate and one may enter a regime where hT( 1 — a) is larger than 2, so the apparent activation energy will drop to that given by equation 12.3.85 (approximately half the value for the intrinsic reaction). As the temperature increases further, the Thiele modulus [hT( 1 — a)] continues to increase with a concomitant decrease in the effectiveness with which the catalyst surface area is used and in the depth to which the reactants are capable of... 

When the effectiveness factors for both reactions approach unity, the selectivity for two independent simultaneous reactions is the ratio of the two intrinsic reaction-rate constants. However, at low values of both effectiveness factors, the selectivity of a porous catalyst may be greater than or less than that for a plane-catalyst surface. For a porous spherical catalyst at large values of the Thiele modulus s, the effectiveness factor becomes inversely proportional to (j>S9 as indicated by equation 12.3.68. In this situation, equation 12.3.133 becomes... 

For comparison reasons, the results derived from the simulation were additionally calculated by means of the Thiele modulus (Equation 12.12), i.e., for a simple first-order reaction. The reaction rate used in the model is more complex (see Equation 12.14) thus, the surface-related rate constant kA in Equation 12.12 is replaced by... 

The presence (or absence) of pore-diffusion resistance in catalyst particles can be readily determined by evaluation of the Thiele modulus and subsequently the effectiveness factor, if the intrinsic kinetics of the surface reaction are known. When the intrinsic rate law is not known completely, so that the Thiele modulus cannot be calculated, there are two methods available. One method is based upon measurement of the rate for differing particle sizes and does not require any knowledge of the kinetics. The other method requires only a single measurement of rate for a particle size of interest, but requires knowledge of the order of reaction. We describe these in turn. 

For an nth-order surface reaction of species A, the rate and Thiele modulus, respectively are... 

Another way in which catalyst deactivation may affect performance is by blocking catalyst pores. This is particularly prevalent during fouling, when large aggregates of materials may be deposited upon the catalyst surface. The resulting increase in diffu-sional resistance may dramatically increase the Thiele modulus, and reduce the effectiveness factor for the reaction. In extreme cases, the pressure drop through a catalyst bed may also increase dramatically. 

This example illustrates calculation of the rate of a surface reaction from an intrinsic-rate law of the LH type in conjunction with determination of the effectiveness factor (rj) from the generalized Thiele modulus (G) and Figure 8.11 as an approximate representation of the 7]-Q relation. We first determine G, then 17, and finally (—rA)obs. 

In the case that the chemical reaction proceeds much faster than the diffusion of educts to the surface and into the pore system a starvation with regard to the mass transport of the educt is the result, diffusion through the surface layer and the pore system then become the rate limiting steps for the catalytic conversion. They generally lead to a different result in the activity compared to the catalytic materials measured under non-diffusion-limited conditions. Before solutions for overcoming this phenomenon are presented, two more additional terms shall be introduced the Thiele modulus and the effectiveness factor. 

The affect of diffusion on catalyst selectivity in porous catalysts operating under non-isothermal conditions has been examined by a number of workers. The mathematical problem has been comprehensively stated in a paper [21] which also takes into account the affect of surface diffusion on selectivity. For consecutive first-order exothermic reactions, the selectivity increases with an increase in Thiele modulus when the parameter A (the difference between the activation energy for reaction... 

Thus we have expressions for the effectiveness factor for different catalyst geometries. The Thiele modulus can be computed from catalyst geometry and surface area parameters. The characteristic size is 21 for a porous slab and 2R for a cylinder or sphere. While the expressions for r)(0) appear quite different, they are in fact very similar when scaled appropriately, and they have the same asymptotic behavior,... 

When dealing with two-dimensional formation of patterns in lipidic-proteic membranes (fluid membranes), not only does the coupling between the chemical reaction in the membrane and the surface diffusion have to be considered (i.e., the Thiele modulus), but one must also consider the coupling with the onset of convection (Navier-Stokes equa-... 

The Thiele moduli for the cylinder and sphere differ from that for the slab. In the case of the slab we recall that = XL, whereas for the cylinder it is conveniently defined as 0 = Xr0/2 and for the sphere as = Xro/3. In each case the reciprocal of this corresponds to the respective asymptote for the curve representing the slab, cylinder or sphere. We may note here that the ratio of the geometric volume V p of each of the models to the external surface area Sx is L for the slab, ro/2 for the cylinder and ro/3 for the sphere. Thus, if the Thiele modulus is defined as ... 

To have a quantitative idea of the problem of intraparticle diffusion, effectiveness factors for the two catalysts were calculated from the observed second order rate constants (based on surface area) using the "triangle method" suggested by Saterfield (4). The effectiveness factors for Monolith and Nalcomo 474 catalysts on Synthoil liquid at 371°C (700 F) were calculated to be 0.94 and 0.216, respectively. In applying the relationship between the "Thiele Modulus," 4>> and the "effectiveness factor," n> the following simplifying assumptions were made ... 

The well known Thiele modulus of the reaction. This is defined as the ratio of the intrinsic chemical rate, calculated at bulk fluid phase conditions, to the maximum rate of effective diffusion at the external pellet surface. For spherical catalyst pellets, the Thiele modulus is given by... 

However, the boundary condition at the external pellet surface is now defined by eq 36 instead of eq 38. As a consequence, a different expression for the integration constant C results, which is not only a function of the Thiele modulus , but also depends on the Biot number for mass transport Bim. Hence, a complete characterization of this problem already requires two parameters. 

To derive an equation for determining the overall effectiveness factor, we first introduce a Thiele modulus which is related to the unknown surface temperature Ts ... 

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