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Factor effective diffusion

Xu and Froment (1989b) developed the most widely accepted kinetic model, deriving the intrinsic parameters and incorporating diffusional limitations through the evaluation of the tortuosity factor, effective diffusivities, and the effectiveness factor. These parameters were used in the simulation of commercial reactors and industrial steam reformers with satisfactory results. [Pg.451]

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). [Pg.516]

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. [Pg.172]

The mass transport influence is easy to diagnose experimentally. One measures the rate at various values of the Thiele modulus the modulus is easily changed by variation of R, the particle size. Cmshing and sieving the particles provide catalyst samples for the experiments. If the rate is independent of the particle size, the effectiveness factor is unity for all of them. If the rate is inversely proportional to particle size, the effectiveness factor is less than unity and

experimental points allow triangulation on the curve of Figure 10 and estimation of Tj and ( ). It is also possible to estimate the effective diffusion coefficient and thereby to estimate Tj and ( ) from a single measurement of the rate (48). [Pg.172]

For the effective diffusivity in pores, De = (0/t)D, the void fraction 0 can be measured by a static method to be between 0.2 and 0.7 (Satterfield 1970). The tortuosity factor is more difficult to measure and its value is usually between 3 and 8. Although a preliminary estimate for pore diffusion limitations is always worthwhile, the final check must be made experimentally. Major results of the mathematical treatment involved in pore diffusion limitations with reaction is briefly reviewed next. [Pg.25]

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. [Pg.635]

The effectiveness factor depends, not only on the reaction rate constant and the effective diffusivity, but also on the size and shape of the catalyst pellets. In the following analysis detailed consideration is given to particles of two regular shapes ... [Pg.635]

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. [Pg.645]

Suppose that catalyst pellets in the shape of right-circular cylinders have a measured effectiveness factor of r] when used in a packed-bed reactor for a first-order reaction. In an effort to increase catalyst activity, it is proposed to use a pellet with a central hole of radius i /, < Rp. Determine the best value for RhjRp based on an effective diffusivity model similar to Equation (10.33). Assume isothermal operation ignore any diffusion limitations in the central hole, and assume that the ends of the cylinder are sealed to diffusion. You may assume that k, Rp, and eff are known. [Pg.379]

Another important factor in diffusion measurements that is often encountered in NMR experiments is the effect of time on diffusion coefficients. For example, Kinsey et al. [195] found water diffusion coefficients in muscles to be time dependent. The effects of diffusion time can be described by transient closure problems within the framework of the volume averaging method [195,285]. Other methods also account for time effects [204,247,341]. [Pg.584]

In this exercise we shall estimate the influence of transport limitations when testing an ammonia catalyst such as that described in Exercise 5.1 by estimating the effectiveness factor e. We are aware that the radius of the catalyst particles is essential so the fused and reduced catalyst is crushed into small particles. A fraction with a narrow distribution of = 0.2 mm is used for the experiment. We shall assume that the particles are ideally spherical. The effective diffusion constant is not easily accessible but we assume that it is approximately a factor of 100 lower than the free diffusion, which is in the proximity of 0.4 cm s . A test is then made with a stoichiometric mixture of N2/H2 at 4 bar under the assumption that the process is far from equilibrium and first order in nitrogen. The reaction is planned to run at 600 K, and from fundamental studies on a single crystal the TOP is roughly 0.05 per iron atom in the surface. From Exercise 5.1 we utilize that 1 g of reduced catalyst has a volume of 0.2 cm g , that the pore volume constitutes 0.1 cm g and that the total surface area, which we will assume is the pore area, is 29 m g , and that of this is the 18 m g- is the pure iron Fe(lOO) surface. Note that there is some dispute as to which are the active sites on iron (a dispute that we disregard here). [Pg.430]

It should be mentioned here that a different definition of the diffusion coefficient is often used in chemical engineering problems, which is more appropriate for the description of reactant or tracer transport. It takes into account the fact that the total fluid contained in a porous substance of porosity e is reduced by this factor relative to the bulk, so that an effective diffusion coefficient D of the reactants is defined such that... [Pg.271]

Parenteral products should be formulated to possess sufficient buffer capacity to maintain proper product pH. Factors that influence pH include product degradation, container and stopper effects, diffusion of gases through the closure, and the effect of gases in the product or in the headspace. However, the buffer capacity of a formulation must be readily overcome by the biological fluids thus, the concentration and ratios of buffer ingredients must be carefully selected. [Pg.394]

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. [Pg.432]

For the purposes of this illustrative example, we wish to calculate the combined and effective diffusivities of cumene in a mixture of benzene and cumene at 1 atm total pressure and 510 °C within the pores of a typical TCC (Thermofor Catalytic Cracking) catalyst bead. For our present purposes, the approximation to the combined diffusivity given by equation 12.2.8 will be sufficient because we will see that the Knudsen diffusion term is the dominant factor in determining the combined diffusivity. [Pg.437]

The Effectiveness Factor Analysis in Terms of Effective Diffusivities First-Order Reactions on Spherical Pellets. Useful expressions for catalyst effectiveness factors may also be developed in terms of the concept of effective diffusivities. This approach permits one to write an expression for the mass transfer within the pellet in terms of a form of Fick s first law based on the superficial cross-sectional area of a porous medium. We thereby circumvent the necessity of developing a detailed mathematical model of the pore geometry and size distribution. This subsection is devoted to an analysis of simultaneous mass transfer and chemical reaction in porous catalyst pellets in terms of the effective diffusivity. In order to use the analysis with confidence, the effective diffusivity should be determined experimentally, since it is difficult to obtain accurate estimates of this parameter on an a priori basis. [Pg.447]

Illustration 12.3 indicates the use of the effective diffusivity approach for estimating catalyst effectiveness factors when this parameter is determined experimentally or may be estimated. [Pg.449]

ILLUSTRATION 12.3 DETERMINATION OF CATALYST EFFECTIVENESS FACTOR FOR THE CUMENE CRACKING REACTION USING THE EFFECTIVE DIFFUSIVITY APPROACH Use the effective diffusivity approach to evaluate the effectiveness factor for the silica-alumina catalyst pellets considered in Illustration 12.2. [Pg.449]

Effectiveness factor plot for spherical catalyst particles based on effective diffusivities (first-order reaction). [Pg.450]

The measured value of k Sg is 0.716 cm3/(sec-g catalyst) and the ratio of this value to k ltTueSg should be equal to our assumed value for the effectiveness factor, if our assumption was correct. The actual ratio is 0.175, which is at variance with the assumed value. Hence we pick a new value of rj and repeat the procedure until agreement is obtained. This iterative approach produces an effectiveness factor of 0.238, which corresponds to a differs from the experimental value (0.17) and that calculated by the cylindrical pore model (0.61). In the above calculations, an experimental value of eff was not available and this circumstance is largely responsible for the discrepancy. If the combined diffusivity determined in Illustration 12.1 is converted to an effective diffusivity using equation 12.2.9, the value used above corresponds to a tortuosity factor of 2.6. If we had employed Q)c from Illustration 12.1 and a tortuosity factor of unity to calculate eff, we would have determined that rj = 0.65, which is consistent with the value obtained from the straight cylindrical pore model in Illustration 12.2. [Pg.450]

The Effectiveness Factor Analysis in Terms of Effective Diffusivities Extension to Reactions Other than First-Order and Various Catalyst Geometries. The analysis developed in Section 12.3.1.3 may be extended in relatively simple straightforward fashion to other integer-order rate expressions and to other catalyst geometries such as flat plates and cylinders. Some of the key results from such extensions are treated briefly below. [Pg.450]

When the hydrogen pressure is 1 atm, and the temperature is 77 °K, the experimentally observed (apparent) rate constant is 0.159 cm3/ sec-g catalyst. Determine the mean pore radius, the effective diffusivity of hydrogen, and the catalyst effectiveness factor. [Pg.526]

To employ this relation one needs to estimate a tortuosity factor in order to convert the combined diffusivity to an effective diffusivity by equation 12.2.9. If we assume a value of 3, then... [Pg.562]

For diffusion in the soil air-pores, a molecular diffusivity of 0.02 m2/h is reduced to an effective diffusivity using a Millington-Quirk type of relationship by a factor of about 20 to 10-3 m2/h. Combining this with a path length of 0.05 m gives an effective air-to-soil mass transfer coefficient kSA of 0.02 m/h, which is designated as U5. [Pg.24]

Similarly, for diffusion in water a molecular diffusivity of 2 x 10-6 m2/h is reduced by a factor of 20 to an effective diffusivity of 10 7 m2/h, which is combined with a path length of 0.05 m to give an effective soil-to-water mass transfer coefficient of ksw 2 x 10 6 m/h. [Pg.24]

Fig. 16. Panorama of values in the literature for diffusion coefficients of hydrogen in silicon and for other diffusion-related descriptors. Black symbols represent what can plausibly be argued to be diffusion coefficients of a single species or of a mixture of species appropriate to intrinsic conditions. Other points are effective diffusion coefficients dependent on doping and hydrogenation conditions polygons represent values inferred from passivation profiles [i.e., similar to the Dapp = L2/t of Eq. (95) and the ensuing discussion] pluses and crosses represent other quantities that have been called diffusion coefficients. The full line is a rough estimation for H+, drawn assuming the top points to refer mainly to this species otherwise the line should be higher at this end. The dashed line is drawn parallel a factor 2 lower to illustrate a plausible order of magnitude of the difference between 2H and H. Fig. 16. Panorama of values in the literature for diffusion coefficients of hydrogen in silicon and for other diffusion-related descriptors. Black symbols represent what can plausibly be argued to be diffusion coefficients of a single species or of a mixture of species appropriate to intrinsic conditions. Other points are effective diffusion coefficients dependent on doping and hydrogenation conditions polygons represent values inferred from passivation profiles [i.e., similar to the Dapp = L2/t of Eq. (95) and the ensuing discussion] pluses and crosses represent other quantities that have been called diffusion coefficients. The full line is a rough estimation for H+, drawn assuming the top points to refer mainly to this species otherwise the line should be higher at this end. The dashed line is drawn parallel a factor 2 lower to illustrate a plausible order of magnitude of the difference between 2H and H.
Effective concentration, 23 91 Effective diffusivity, 7 44 75 729-730 Effectiveness factor... [Pg.298]

Initially, a small current, called residual current, flows and continues till the decomposition potential of reducible ionic species is reached. A further increase in applied potential increases the current linearly and reaches to a maximum value called limiting current. Three factors effect the current that during the electrolysis are (i) migration or an electrical effect which depends upon the charge and transference number of the electroactive species, (ii) diffusion of all charged and uncharged species in solution between the... [Pg.40]

The catalyst activity depends not only on the chemical composition but also on the diffusion properties of the catalyst material and on the size and shape of the catalyst pellets because transport limitations through the gas boundary layer around the pellets and through the porous material reduce the overall reaction rate. The influence of gas film restrictions, which depends on the pellet size and gas velocity, is usually low in sulphuric acid converters. The effective diffusivity in the catalyst depends on the porosity, the pore size distribution, and the tortuosity of the pore system. It may be improved in the design of the carrier by e.g. increasing the porosity or the pore size, but usually such improvements will also lead to a reduction of mechanical strength. The effect of transport restrictions is normally expressed as an effectiveness factor q defined as the ratio between observed reaction rate for a catalyst pellet and the intrinsic reaction rate, i.e. the hypothetical reaction rate if bulk or surface conditions (temperature, pressure, concentrations) prevailed throughout the pellet [11], For particles with the same intrinsic reaction rate and the same pore system, the surface effectiveness factor only depends on an equivalent particle diameter given by... [Pg.319]

For those readers requiring further information on the factors effecting the kinetic versus diffusion control of the SSP process, this has been reported by several authors (for example, kinetic aspects [4, 8, 20] and diffusion-influenced aspects [5-7, 9, 11-13, 15]). [Pg.205]


See other pages where Factor effective diffusion is mentioned: [Pg.240]    [Pg.172]    [Pg.245]    [Pg.180]    [Pg.566]    [Pg.577]    [Pg.225]    [Pg.292]    [Pg.331]    [Pg.503]    [Pg.435]    [Pg.469]    [Pg.473]    [Pg.568]    [Pg.153]    [Pg.247]    [Pg.243]    [Pg.731]    [Pg.733]    [Pg.171]   
See also in sourсe #XX -- [ Pg.77 ]




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