Thiele modulus reaction

Thiele modulus in a cylindrical pellet for a first-order reaction. Thiele modulus in a flat plate for a first-order reaction. 

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 result is shown in Figure 10, which is a plot of the dimensionless effectiveness factor as a function of the dimensionless Thiele modulus ( ), which is R.(k/Dwhere R is the radius of the catalyst particle and k is the reaction rate constant. The effectiveness factor is defined as the ratio of the rate of the reaction divided by the rate that would be observed in the absence of a mass transport influence. The effectiveness factor would be unity if the catalyst were nonporous. Therefore, the reaction rate is... 

Figure 10 shows that Tj is a unique function of the Thiele modulus. When the modulus ( ) is small (- SdSl), the effectiveness factor is unity, which means that there is no effect of mass transport on the rate of the catalytic reaction. When ( ) is greater than about 1, the effectiveness factor is less than unity and the reaction rate is influenced by mass transport in the pores. When the modulus is large (- 10), the effectiveness factor is inversely proportional to the modulus, and the reaction rate (eq. 19) is proportional to k ( ), which, from the definition of ( ), implies that the rate and the observed reaction rate constant are proportional to (1 /R)(f9This result shows that both the rate constant, ie, a measure of the intrinsic activity of the catalyst, and the effective diffusion coefficient, ie, a measure of the resistance to transport of the reactant offered by the pore stmcture, influence the rate. It is not appropriate to say that the reaction is diffusion controlled it depends on both the diffusion and the chemical kinetics. In contrast, as shown by equation 3, a reaction in solution can be diffusion controlled, depending on D but not on k. 

Example 5 Application of Effectiveness For a second-order reaction in a plug flow reactor the Thiele modulus is ( ) = SVQ, and inlet concentration is C50 = 1.0. The equation will he integrated for 80 percent conversion with Simpsons rule. Values of T) are... 

Adiabatic Reactions Aside from the Thiele modulus, two other parameters are necessary in this case ... 

No industrially significant reaction has 3 > 0,3 (or with y = 20, and D/a = 1, 5 > 5) and only above this value are the interesting S-shaped curves possible. Of the three values of T, the effectiveness at one value of the Thiele modulus < >, the middle one is an artificial, non-existent solution. The two other values for T show the possibility of discontinuity inside the pellet. While this is possible, it is very unlikely to occur. 

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). 

Figure 2.1 Dependence of the effectiveness factor on the Thiele modulus for a first-order irreversible reaction. Steady-state diffusion and reaction, slab model, and isothermal conditions are assumed.

Most of the actual reactions involve a three-phase process gas, liquid, and solid catalysts are present. Internal and external mass transfer limitations in porous catalyst layers play a central role in three-phase processes. The governing phenomena are well known since the days of Thiele [43] and Frank-Kamenetskii [44], but transport phenomena coupled to chemical reactions are not frequently used for complex organic systems, but simple - often too simple - tests based on the use of first-order Thiele modulus and Biot number are used. Instead, complete numerical simulations are preferable to reveal the role of mass and heat transfer at the phase boundaries and inside the porous catalyst particles. 

Fluid flow and reaction engineering problems represent a rich spectrum of examples of multiple and disparate scales. In chemical kinetics such problems involve high values of Thiele modulus (diffusion-reaction problems), Damkohler and Peclet numbers (diffusion-convection-reaction problems). For fluid flow problems a large value of the Mach number, which represents the ratio of flow velocity to the speed of sound, indicates the possibility of shock waves a large value of the Reynolds number causes boundary layers to be formed near solid walls and a large value of the Prandtl number gives rise to thermal boundary layers. Evidently, the inherently disparate scales for fluid flow, heat transfer and chemical reaction are responsible for the presence of thin regions or "fronts in the solution. 

The internal effectiveness factor is a function of the generalized Thiele modulus (see for instance Krishna and Sie (1994), Trambouze et al. (1988), and Fogler (1986). For a first-order reaction ... 

Figure 3.32. Interna effectiveness factor as a function of the generalized Thiele modulus for a first order reaction.

Fig. 5.4-14. Effectiveness factor versus Thiele modulus for first-order reaction.

Microlevel. The starting point in multiphase reactor selection is the determination of the best particle size (catalyst particles, bubbles, and droplets). The size of catalyst particles should be such that utilization of the catalyst is as high as possible. A measure of catalyst utilization is the effectiveness factor q (see Sections 3.4.1 and 5.4.3) that is inversely related to the Thiele modulus (Eqn. 5.4-78). Generally, the effectiveness factor for Thiele moduli less than 0.5 are sufficiently high, exceeding 0.9. For the reaction under consideration, the particles size should be so small that these limits are met. 

In order to characterize the erosion properties of specific systems, the Thiele modulus 0 has been used to describe those systems where chemical reaction and transport are both important. By making the above Equations (1 - 4) dimensionless, several Thiele moduli are noted. The one which describes the transport of water compared to its consumption by chemical reaction is... 

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... 

The numerator of the right side of this equation is equal to the chemical reaction rate that would prevail if there were no diffusional limitations on the reaction rate. In this situation, the reactant concentration is uniform throughout the pore and equal to its value at the pore mouth. The denominator may be regarded as the product of a hypothetical diffusive flux and a cross-sectional area for flow. The hypothetical flux corresponds to the case where there is a linear concentration gradient over the pore length equal to C0/L. The Thiele modulus is thus characteristic of the ratio of an intrinsic reaction rate in the absence of mass transfer limitations to the rate of diffusion into the pore under specified conditions. 

Figure 12.2 is a plot of the effectiveness factor r] versus the Thiele modulus hT. For low values of hT (slow reaction, rapid diffusion), the effectiveness factor approaches unity. For values of the Thiele modulus above 2.0, tanh hT 1 and the effectiveness factor may be approximated by... 

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. 

Figure 12.7 adapted from Satterfield (40) contains a plot of the effectiveness factor for a zero-order reaction versus the Thiele modulus... 

The analyses of simultaneous reaction and mass transfer in this geometry are similar mathematically to those of the straight cylindrical pore model considered previously, because both are essentally one-dimensional models. In the general case, the Thiele modulus for semiinfinite, flat-plate problems becomes... 

In the limit of low effectiveness factors where tj becomes inversely proportional to the Thiele modulus, the apparent order of the reaction may differ from the true order. In this case, since the rate is proportional to the product of the effectiveness factor and the external concentration... 

In terms of the equilibrium constant for the reaction, the Thiele modulus becomes... 

Since the factor (K + 1 )/K is always greater than unity, Lrev will always be greater (and r less) than the corresponding Thiele modulus for the forward reaction alone, other conditions remaining constant. 

The reactor feed mixture was "prepared so as to contain less than 17% ethylene (remainder hydrogen) so that the change in total moles within the catalyst pore structure would be small. This reduced the variation in total pressure and its effect on the reaction rate, so as to permit comparison of experiment results with theoretical predictions [e.g., those of Weisz and Hicks (61)]. Since the numerical solutions to the nonisothermal catalyst problem also presumed first-order kinetics, they determined the Thiele modulus by forcing the observed rate to fit this form even though they recognized that a Hougen-Watson type rate expression would have been more appropriate. Hence their Thiele modulus was defined as... 

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