Mass transfer resistance reaction

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. 

The enhanced rate expressions for regimes 3 and 4 have been presented (48) and can be appHed (49,50) when one phase consists of a pure reactant, for example in the saponification of an ester. However, it should be noted that in the more general case where component C in equation 19 is transferred from one inert solvent (A) to another (B), an enhancement of the mass-transfer coefficient in the B-rich phase has the effect of moving the controlling mass-transfer resistance to the A-rich phase, in accordance with equation 17. Resistance in both Hquid phases is taken into account in a detailed model (51) which is apphcable to the reversible reactions involved in metal extraction. This model, which can accommodate the case of interfacial reaction, has been successfully compared with rate data from the Hterature (51). 

Asymptotic Solution Rate equations for the various mass-transfer mechanisms are written in dimensionless form in Table 16-13 in terms of a number of transfer units, N = L/HTU, for particle-scale mass-transfer resistances, a number of reaction units for the reaction kinetics mechanism, and a number of dispersion units, Np, for axial dispersion. For pore and sohd diffusion, q = / // p is a dimensionless radial coordinate, where / p is the radius of the particle, if a particle is bidisperse, then / p can be replaced by the radius of a suoparticle. For prehminary calculations. Fig. 16-13 can be used to estimate N for use with the LDF approximation when more than one resistance is important. 

Correlations of heat and mass-transfer rates are fairly well developed and can be incorporated in models of a reaction process, but the chemical rate data must be determined individually. The most useful rate data are at constant temperature, under conditions where external mass transfer resistance has been avoided, and with small particles... 

Many reactions of solids are industrially feasible only at elevated temperatures which are often obtained by contact with combustion gases, particularly when the reaction is done on a large scale. A product of reaction also is often a gas that must diffuse away from a remaining solid, sometimes through a solid product. Thus, thermal and mass-transfer resistances are major factors in the performance of solid reactions. 

In processing, it is frequently necessary to separate a mixture into its components and, in a physical process, differences in a particular property are exploited as the basis for the separation process. Thus, fractional distillation depends on differences in volatility. gas absorption on differences in solubility of the gases in a selective absorbent and, similarly, liquid-liquid extraction is based on on the selectivity of an immiscible liquid solvent for one of the constituents. The rate at which the process takes place is dependent both on the driving force (concentration difference) and on the mass transfer resistance. In most of these applications, mass transfer takes place across a phase boundary where the concentrations on either side of the interface are related by the phase equilibrium relationship. Where a chemical reaction takes place during the course of the mass transfer process, the overall transfer rate depends on both the chemical kinetics of the reaction and on the mass transfer resistance, and it is important to understand the relative significance of these two factors in any practical application. 

When the mass transfer resistance within the particle is significant, a concentration gradient of reactant is established within the particle, with the concentration, and hence the reaction rate, decreasing progressively with distance from the particle surface. The overall reaction rate is therefore less than that given by equation 10.195. 

The ratio of the overall rate of reaction to that which would be achieved in the absence of a mass transfer resistance is referred to as the effectiveness factor rj. SCOTT and Dullion(29) describe an apparatus incorporating a diffusion cell in which the effective diffusivity De of a gas in a porous medium may be measured. This approach allows for the combined effects of molecular and Knudsen diffusion, and takes into account the effect of the complex structure of the porous solid, and the influence of tortuosity which affects the path length to be traversed by the molecules. 

This is a transitional region in which reaction kinetics and mass transfer resistance both affect the overall reaction rate. 

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

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. 

In a continuous steady state reactor, a slightly soluble gas is absorbed into a liquid in which it dissolves and reacts, the reaction being second order with respect to the dissolved gas. Calculate the reaction rate constant on the assumption that the liquid is semi-infinite in extent and that mass transfer resistance in the gas phase is negligible. The diffusivity of the gas in the liquid is 10" 8 m2/s, the gas concentration in the liquid falls to one half of its value in the liquid over a distance of 1 mm, and the rate of absorption at the interface is 4 x 10"6 kmol/m2 s. 

A final, obvious but important, caution about catalyst film preparation Its thickness and surface area Ac must be low enough, so that the catalytic reaction under study is not subject to external or internal mass transfer limitations within the desired operating temperature range. Direct impingement of the reactant stream on the catalyst surface1,19 is advisable in order to diminish the external mass transfer resistance. 

Equation (10.29) is the appropriate reaction rate to use in global models such as Equation (10.1). The reaction rate would be —ka if there were no mass transfer resistance. The effectiveness factor rj accounts for pore diffusion and him resistance so that the effective rate is — 7ka. 

Reactions other than hrst order can be treated numerically, but a priori predictions of effectiveness factors are rarely possible, even for the simple cases considered here. The approach of Examples 10.6 through 10.8 can sometimes be used to estimate whether mass transfer resistances are important. When mass transfer is important, effectiveness factors are determined experimentally. 

Some deactivation processes lower the number of active sites So- Others add mass transfer resistances. In either case, they cause a reduction in the reaction rate that is reflected in a time-dependent effectiveness factor ... 

Example 11.8 With highly reactive absorbents, the mass transfer resistance in the gas phase can be controlling. Determine the number of trays needed to reduce the CO2 concentration in a methane stream from 5% to 100 ppm (by volume), assuming the liquid mass transfer and reaction steps are fast. A 0.9-m diameter column is to be operated at 8 atm and 50°C with a gas feed rate of 0.2m /s. The trays are bubble caps operated with a 0.1-m liquid level. Literature correlations suggest = 0.002 m/s and A, = 20m per square meter of tray area. 

The diffusivity in gases is about 4 orders of magnitude higher than that in liquids, and in gas-liquid reactions the mass transfer resistance is almost exclusively on the liquid side. High solubility of the gas-phase component in the liquid or very fast chemical reaction at the interface can change that somewhat. The Sh-number does not change very much with reactor design, and the gas-liquid contact area determines the mass transfer rate, that is, bubble size and gas holdup will determine reactor efficiency. 

It is remarkable that the falling film micro reactor achieved complete conversion for all process variations applied [5]. This is unlike conventional reactor operation reported for this reaction, displaying pronounced mass transfer resistance. 

As the agitation of the reaction mixture was very intensive, interfacial mass transfer resistance is suppressed, and the concentration in gas and liquid are related by the phase equilibrium... 

When fluid velocities are high relative to the solid, mass transfer is rapid. However, in stagnant regions or in batch reactors where no provision is made for agitation, one may encounter cases where mass transfer limits the observed reaction rate. We should also note that in industrial practice pressure drop constraints may make it impractical to employ the exceedingly high velocities necessary to overcome the mass transfer resistance associated with highly active catalysts. 

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