Pellets, mass transfer

Evaluate the performance of the catalytic converter in converting CO and propylene. Determine the amount of catalyst required to convert 99.6% of the CO and propylene. The reaction chemistry and pellet mass-transfer parameters are given in. Table 7.5. The feed. conditions. and hea.t.-transfer parameters. are. given. in. Table 7,6,. 

HoUewand, M.P. and L.F. Gladden, Visualization of phases in catalyst peUets and pellet mass transfer processes using magnetic resonance imaging. Trans IChemE, 70A pp. 183-185, 1992. 

Though the case of constant matrix elements and the example investigated by Hite are the only situations for which Che stoichiometric relations have been fully established in pellets of arbitrary shape, it is worth mentioning situations in which these relations are known not to hold. When the composition and pressure at the surface of the pellet may vary in an arbitrary way from point to point it seems unlikely on intuitive grounds that equations (11.3) will be satisfied, and Hite and Jackson [77] confirmed by direct computation that there are, indeed, simple situations in which they are violated. Less obviously, direct computation [75] has also shown them to be violated even when the pressure and composition of the environment are the same everywhere, in the case where finite resistances to mass transfer exist at the surface of Che pellet. 

A proper resolution of Che status of Che stoichiometric relations in the theory of steady states of catalyst pellets would be very desirable. Stewart s argument and the other fragmentary results presently available suggest they may always be satisfied for a single reaction when the boundary conditions correspond Co a uniform environment with no mass transfer resistance at the surface, regardless of the number of substances in Che mixture, the shape of the pellet, or the particular flux model used. However, this is no more than informed and perhaps wishful speculation. 

When the catalyst is expensive, the inaccessible internal surface is a liabihty, and in every case it makes for a larger reactor size. A more or less uniform pore diameter is desirable, but this is practically reahz-able only with molecular sieves. Those pellets that are extrudates of compacted masses of smaller particles have bimodal pore size distributions, between the particles and inside them. Micropores have diameters of 10 to 100 A, macropores of 1,000 to 10,000 A. The macropores provide rapid mass transfer into the interstices that lead to the micropores where the reaction takes place. 

The three principal catalyst bed configurations are the pellet bed, the monolith, and the metallic wire meshes. An open structure with large openings is needed to fulfill the requirement of a low pressure drop even at the very high space velocities of 200,000 hr-1. On the other hand, packings with small diameters would provide more external surface area to fulfill the requirement for rapid mass transfer from the g .s stream to the solid surface. The compromise between these two ideals results in a rather narrow range of dimensions pellets are from to 1 in. in diameter, monoliths have 6 to 20 channels/in., and metallic meshes have diameters of about 0.004 to 0.03 in. 

The correlation studies of heat and mass transfer in pellet beds have been investigated by many, usually in terms of the. /-factors (113-115). According to Chilton and Colburn the two. /-factors are equal in value to one half of the Fannings friction factor / used in the calculation of pressure drop. The. /-factors depend on the Reynolds number raised to a factor varying from —0.36 to —0.68, so that the Nusselt number depends on the Reynolds number raised to a factor varying from 0.64 to 0.32. In the range of the Reynolds number from 10 to 170 in the pellet bed, jd should vary from 0.5 to 0.1, which yields a Nusselt number from 4.4 to 16.1. The heat and mass transfer to wire meshes has received much less attention (110,116). The correlation available shows that the /-factor varies as (Re)-0-41, so that the Nusselt number varies as (Re)0-69. In the range of the Reynolds number from 20 to 420, the j-factor varies from 0.2 to 0.05, so that the Nusselt number varies from 3.6 to 18.6. The Sherwood number for CO is equal to 1.05 Nu, but the Sherwood number for benzene is 1.31 Nu. 

Provided that the catalyst is active enough, there will be sufficient conversion of the pollutant gases through the pellet bed and the screen bed. The Sherwood number of CO is almost equal to the Nusselt number, and 2.6% of the inlet CO will not be converted in the monolith. The diffusion coefficient of benzene is somewhat smaller, and 10% of the inlet benzene is not converted in the monolith, no matter how active is the catalyst. This mass transfer limitation can be easily avoided by forcing the streams to change flow direction at the cost of some increased pressure drop. These calculations are comparable with the data in Fig. 22, taken from Carlson 112). 

Naturally, there are two more Peclet numbers defined for the transverse direction dispersions. In these ranges of Reynolds number, the Peclet number for transverse mass transfer is 11, but the Peclet number for transverse heat transfer is not well agreed upon (121, 122). None of these dispersions numbers is known in the metal screen bed. A special problem is created in the monolith where transverse dispersion of mass must be zero, and the parallel dispersion of mass can be estimated by the Taylor axial dispersion theory (123). The dispersion of heat would depend principally on the properties of the monolith substrate. Often, these Peclet numbers for individual pellets are replaced by the Bodenstein numbers for the entire bed... 

MASS TRANSFER AND CHEMICAL REACTION IN A CATALYST PELLET... 

In general, the concentration of the reactant will decrease from CAo in the bulk of the fluid to CAi at the surface of the particle, to give a concentration driving force of CAo - CAi)-Thus, within the pellet, the concentration will fall progressively from CAi with distance from the surface. This presupposes that no distinct adsorbed phase is formed in the pores. In this section the combined effects of mass transfer and chemical reaction within the particle are considered, and the effects of external mass transfer are discussed in Section J 0.8.4. 

If there were no resistance to mass transfer, the concentration of A would be equal to CAi everywhere in the pellet and the reaction rate per unit area in the half-pellet (of volume... 

Thus the mass transfer at the outer surface of the pellet (moles/unit time) is ... 

With no resistance to mass transfer, the concentration is Cm throughout the whole spherical pellet, and the reaction rate, which must be equal to the mass transfer rate in a steady-state process, is ... 

Mass transfer and chemical reaction with a mass transfer resistance external to the pellet... 

When the resistance to mass transfer to the external surface of the pellet is significant compared with that within the particle, part of the concentration driving force is required to overcome this external resistance, and the concentration of reacting material at the surface of the pellet Cm is less than that in the bulk of the fluid phase Cao- In Sections 10.7.1-10.7.3, the effect of mass transfer resistance within a porous particle... 

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. 

It is possible to eliminate the mass transfer resistances in Steps 2, 3, 7, and 8 by grinding the catalyst to a fine powder and exposing it to a high-velocity gas stream. The concentrations of reactants immediately adjacent to the catalytic surface are then equal to the concentrations in the bulk gas phase. The resulting kinetics are known as intrinsic kinetics since they are intrinsic to the catalyst surface and not to the design of the pores, or the pellets, or the reactor. 

In order to verify that the fixed bed and the micro-channel reactor are equivalent concerning chemical conversion, an irreversible first-order reaction A —) B with kinetic constant was considered. For simplicity, the reaction was assumed to occur at the channel surface or at the surface of the catalyst pellets, respectively. Diffusive mass transfer to the surface of the catalyst pellets was described by a correlation given by Villermaux [115]. 

As a second process, the hydrogenation of a-methylstyrene is a standard process for elucidating mass transfer effects in catalyst pellets and in fixed-bed reactors... 

One must understand the physical mechanisms by which mass transfer takes place in catalyst pores to comprehend the development of mathematical models that can be used in engineering design calculations to estimate what fraction of the catalyst surface is effective in promoting reaction. There are several factors that complicate efforts to analyze mass transfer within such systems. They include the facts that (1) the pore geometry is extremely complex, and not subject to realistic modeling in terms of a small number of parameters, and that (2) different molecular phenomena are responsible for the mass transfer. Consequently, it is often useful to characterize the mass transfer process in terms of an effective diffusivity, i.e., a transport coefficient that pertains to a porous material in which the calculations are based on total area (void plus solid) normal to the direction of transport. For example, in a spherical catalyst pellet, the appropriate area to use in characterizing diffusion in the radial direction is 47ir2. 

Bulk or forced flow of the Hagan-Poiseuille type does not in general contribute significantly to the mass transport process in porous catalysts. For fast reactions where there is a change in the number of moles on reaction, significant pressure differentials can arise between the interior and the exterior of the catalyst pellets. This phenomenon occurs because there is insufficient driving force for effective mass transfer by forced flow. Molecular diffusion occurs much more rapidly than forced flow in most porous catalysts. 

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