Examples catalyst effectiveness factor

If the two competing reactions have the same concentration dependence, then the catalyst pore structure does not influence the selectivity because at each point within the pore structure the two reactions will proceed at the same relative rate, independent of the reactant concentration. However, if the two competing reactions differ in the concentration dependence of their rate expressions, the pore structure may have a significant effect on the product distribution. For example, if V is formed by a first-order reaction and IF by a second-order reaction, the observed yield of V will increase as the catalyst effectiveness factor decreases. At low effectiveness factors there will be a significant gradient in the reactant concentration as one moves radially inward. The lower reactant concentration within the pore structure would then... 

Simulation of tubular steam reformers and a comparison with industrial data are shown in many references, such as [250], In most cases the simulations are based on measured outer tube-wall temperatures. In [181] a basic furnace model is used, whereas in [525] a radiation model similar to the one in Section 3.3.6 is used. In both cases catalyst effectiveness factor profiles are shown. Similar simulations using the combined two-dimensional fixed-bed reactor, and the furnace and catalyst particle models described in the previous chapters are shown below using the operating conditions and geometry for the simple steam reforming furnace in the hydrogen plant. Examples 1.3, 2.1 and 3.2. Similar to [181] and [525], the intrinsic kinetic expressions used are the Xu and Froment expressions [525] from Section 3.5.2, but with the parameters from [541]. 

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. 

The concentration and temperature Tg will, for example, be conditions of reactant concentration and temperature in the bulk gas at some point within a catalytic reactor. Because both c g and Tg will vary with position in a reactor in which there is significant conversion, eqns. (1) and (15) have to be coupled with equations describing the reactor environment (see Sect. 6) for the purpose of commerical reactor design. Because of the nonlinearity of the equations, the problem can only be solved in this form by numerical techniques [5, 6]. However, an approximation may be made which gives an asymptotically exact solution [7] or, alternatively, the exponential function of temperature may be expanded to give equations which can be solved analytically [8, 9]. A convenient solution to the problem may be presented in the form of families of curves for the effectiveness factor as a function of the Thiele modulus. Figure 3 shows these curves for the case of a first-order irreversible reaction occurring in spherical catalyst particles. Two additional independent dimensionless paramters are introduced into the problem and these are defined as... 

Another type of stability problem arises in reactors containing reactive solid or catalyst particles. During chemical reaction the particles themselves pass through various states of thermal equilibrium, and regions of instability will exist along the reactor bed. Consider, for example, a first-order catalytic reaction in an adiabatic tubular reactor and further suppose that the reactor operates in a region where there is no diffusion limitation within the particles. The steady state condition for reaction in the particle may then be expressed by equating the rate of chemical reaction to the rate of mass transfer. The rate of chemical reaction per unit reactor volume will be (1 - e)kCAi since the effectiveness factor rj is considered to be unity. From equation 3.66 the rate of mass transfer per unit volume is (1 - e) (Sx/Vp)hD(CAG CAl) so the steady state condition is ... 

The effectiveness factor Tj is the ratio of the rate of reaction in a porous catalyst to the rate in the absence of diffusion (i.e., under bulk conditions). The theoretical basis for q in a porous catalyst has been discussed in Sec. 7. For example, for an isothermal first-order reaction... 

The whole of the internal surface area of a porous catalyst will be available for the catalytic reaction if the rates of diffusion of reactant into the pores, and of product out of them, are fast compared with the rate of the surface reaction. In contrast, if the reactant diffuses slowly but reacts rapidly, conversion to product will occur near the pore entrances and the interior of the pores will play no role in the catalysis. Ion exchange resins are typical examples of catalysts for which such considerations are important (cf. Sect. 2.3). The detailed mathematics of this problem have been treated in several texts [49-51] and we shall now quote some of the main theoretical results derived for isothermal conditions. The parameters involved tend to be those employed by chemical engineers and differ somewhat from those used elsewhere in this chapter. In particular, the catalyst material (active + support) is present in the form of pellets of volume Vp and the catalytic rates vv are given per unit volume of pellet (mols m 3). The decrease in vv brought about by pore diffusion is then expressed by an effectiveness factor, rj, defined by... 

This tutorial paper begins with a short introduction to multicomponent mass transport in porous media. A theoretical development for application to single and multiple reaction systems is presented. Two example problems are solved. The first example is an effectiveness factor calculation for the water-gas shift reaction over a chromia-promoted iron oxide catalyst. The methods applicable to multiple reaction problems are illustrated by solving a steam reformer problem. The need to develop asymptotic methods for application to multiple reaction problems is apparent in this example. 

Example 9.3 Effectiveness factor for first-order irreversible reaction-diffusion system Consider a first-order reaction occurring on the pore walls of a catalyst with equimolar counter diffusion. Assume that isothermal conditions are maintained, and a catalyst with simple slab geometry is used (Figure 9.1). If the -coordinate is oriented from the centerline to the surface, the steady-state reaction diffusion equation for reaction A — B between reactant A and product B is... 

For example, an isothermal, first-order reaction in a flat plate catalyst pellet has individual effectiveness factors that are ... 

It is not easy to compare the activity of the V-W-Ti catalysts here tested with the lot of chromia, Pt and Pd based catalysts previously used because they have different shapes (monoliths and spheres) and because very different particle sizes arc involved (having thus very different effectiveness factors). For conqiarison purposes, all X-T curves were adjusted to a simple fust order kinetic model (with rate based on overall volume of catalyst, both for monoliths and for fixed beds). From the kinetic constants so obtained (see details of the method in ref 7), the preexponential factors (ko) of the Arrhenius law and the apparent energies of activation (E, p) were calculated for all catalysts. One example is shown in Figure 17. By the well Imown compensation effect between ko and E,pp, the kg values so obtained were recalculated for a given E.pp value of 44 kJ/mol. Such new ko value was used [7] as an activity index of the catalyst. 

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