Dispersion coefficient tubular reactors

Axial and radial dispersion or non-ideal flow in tubular reactors is usually characterised by analogy to molecular diffusion, in which the molecular diffusivity is replaced by eddy dispersion coefficients, characterising both radial and longitudinal dispersion effects. In this text, however, the discussion will be limited to that of tubular reactors with axial dispersion only. Otherwise the model equations become too complicated and beyond the capability of a simple digital simulation language. 

Empty tubular reactors often are simulated by the simple plug flow model or by a dispersion model with a small value of the dispersion coefficient. 

Amongst the assumptions we have made in developing the model are the following that Pick s law is applicable to the diffusion processes, the gel particles are isotropic and behave as hard spheres, the flow rate is uniform throughout the bed, the dispersion in the column Ccui be approximated by the use of an axial dispersion coefficient cuid that polymer molecules have an independent existence (i.e. very dilute solution conditions exist within the column). Our approach borrows extensively many of the concepts which have been developed to interpret the behaviour of packed bed tubular reactors (5). 

That notorious pair, the Danckwerts boundary conditions for the tubular reactor, provides a good illustration of boundary conditions arising from nature. Much ink has been spilt over these, particularly the exit condition that Danckwerts based on his (perfectly correct, but intuitive) engineering insight. If we take the steady-state case of the simplest distributed example given previously but make the flux depend on dispersion as well as on convection, then, because there is only one-space dimension,/= vAc — DA dddz), where D is a dispersion coefficient. Then, as the assumption of steady state eliminates... 

The question can be answered by noting that, as the value of D goes to infinity, the tubular reactor becomes more and more completely mixed until in the limit it is a stirred tank. We should therefore be able to get the equations for the stirred tank as a limiting case. At this point, we should really work in dimensionless variables. = zIL is a natural way of reducing the length and, because the residence time is Llv, the dimensionless time is r = tvIL. Note that, by comparing the two models, 8 = Vlq = Llv, Da = kd, and we need the dimensionless dispersion coefficient Pe = vLID. The limit we want is then Pe 0. With u( ) = c(z)/cin and U= cproduct/cin... 

The nature of dispersion. The effect which the solid packing has on the flow pattern within a tubular reactor can sometimes be of sufficient magnitude to cause significant departures from plug flow conditions. The presence of solid particles in a tube causes elements of flowing gas to become displaced randomly and therefore produces a mixing effect. An eddy diffusion coefficient can be ascribed to this mixing effect and becomes superimposed on the transport processes which normally occur in unpacked tubes—either a molecular diffusion process at fairly low Reynolds... 

The model is referred to as a dispersion model, and the value of the dispersion coefficient De is determined empirically based on correlations or experimental data. In a case where Eq. (19-21) is converted to dimensionless variables, the coefficient of the second derivative is referred to as the Peclet number (Pe = uL/De), where L is the reactor length and u is the linear velocity. For plug flow, De = 0 (Pe ) while for a CSTR, De = oo (Pe = 0). To solve Eq. (19-21), one initial condition and two boundary conditions are needed. The closed-ends boundary conditions are uC0 = (uC — DedC/dL)L=o and (dC/BL)i = i = 0 (e.g., see Wen and Fan, Models for Flow Systems in Chemical Reactors, Marcel Dekker, 1975). Figure 19-2 shows the performance of a tubular reactor with dispersion compared to that of a plug flow reactor. 

Tubular Reactor with Dispersion As discussed earlier, a multistage CSTR model can be used to simulate the RTD in pilot and commercial reactors. The dispersion model, similar to Fick s molecular diffusion law with an empirical dispersion coefficient De replacing the diffusion coefficient, may also be used. 

Like axial dispersion, radial dispersion can also occur. Radial-dispersion effects normally arise from radial thermal gradients that can dramatically alter the reaction rate across the diameter of the reactor. Radial dispersion can be described in an analogous manner to axial dispersion. That is, there is a radial dispersion coefficient. A complete material balance for a transient tubular reactor could look like ... 

Here we use a single parameter to account for the nonideality of our reactor. This parameter is most always evaluated by analyzing the RTD determined from a tracer test. Examples of one-parameter models for a nonideal CSTR include the reactor dead volume V, where no reaction takes place, or the fraction / of fluid bypassing the reactor, thereby exiting unreacted. Examples of one-parameter models for tubular reactors include the tanks-in-series model and the dispersion model. For the tanks-in-series model, the parameter is the number of tanks, n, and for the dispersion model, it is the dispersion coefficient D,. Knowing the parameter values, we then proceed to determine the conversion and/or effluent concentrations for the reactor. 

Flow, Reaction, and Dispersion Having discussed how to determine the dispersion coefficient we now return to the case where we have both dispersion and reaction in a tubular reactor. A mole balance is taken on a particular component of the mixture (say, species A) over a short length Ac of a tubular reactor in a maimer identical to that in Chapter I, to arrive at... 

Instead of the partial differential equation model presented above, the model is developed here in dynamic difference equation form, which is suitable for solution by dynamic simulation packages, such as Madonna. Analogous to the previous development for tubular reactors and extraction columns, the development of the dynamic dispersion model starts by considering an element of tube length AZ, with a cross-sectional area of Ac, a superficial flow velocity of V and an axial dispersion coefficient, or diffusivity D. Convective and diffusive flows of component A enter and leave the liquid phase volume of any element, n, as indicated in Fig. 4.24 below. Here j represents the diffusive flux, L the liquid flow rate and and Cla the concentration of any species A in both the solid and liquid phases, respectively. 

In particular cases simplified reactor models can be obtained neglecting the insignificant terms in the governing microscopic equations (without averaging in space) [9]. For axisymmetrical tubular reactors, the species mass and heat balances are written in cylindrical coordinates. Himelblau and Bischoff [9] give a list of simplified models that might be used to describe tubular reactors with steady-state turbulent flow. A representative model, with radially variable velocity profile, and axial- and radial dispersion coefficients, is given below ... 

The axial mixing in a tubular reactor can sometimes be described by a dispersion model. This model is based on the assumption that the RTD may be considered to result from piston flow on which is superimposed an axial dispersion. The latter is taken into account by means of a constant effective axial dispersion coefficient, Dax, which has the same dimensions as the molecular diffusion coefficient, Dm. Usually Dax is much larger than the molecular diffusion coefficient because it incorporates all effects that cause deviations from plug flow, such as variations in radial velocities, eddies, and vortices. 

Notice that the molar density of key-limiting reactant A on the external surface of the catalytic pellet is always used as the characteristic quantity to make the molar density of component i dimensionless in all the component mass balances. This chapter focuses on explicit numerical calculations for the effective diffusion coefficient of species i within the internal pores of a catalytic pellet. This information is required before one can evaluate the intrapellet Damkohler number and calculate a numerical value for the effectiveness factor. Hence, 50, effective is called the effective intrapellet diffusion coefficient for species i. When 50, effective appears in the denominator of Ajj, the dimensionless scaling factor is called the intrapellet Damkohler number for species i in reaction j. When the reactor design focuses on the entire packed catalytic tubular reactor in Chapter 22, it will be necessary to calcnlate interpellet axial dispersion coefficients and interpellet Damkohler nnmbers. When there is only one chemical reaction that is characterized by nth-order irreversible kinetics and subscript j is not required, the rate constant in the nnmerator of equation (21-2) is written as instead of kj, which signifies that k has nnits of (volume/mole)"" per time for pseudo-volumetric kinetics. Recall from equation (19-6) on page 493 that second-order kinetic rate constants for a volnmetric rate law based on molar densities in the gas phase adjacent to the internal catalytic surface can be written as... 

Results from the previous section in this chapter illustrate how and when interpellet axial dispersion plays an important role in the design of packed catalytic tubular reactors. When diffusion is important, more sophisticated numerical techniques are required to solve second-order ODEs with split boundary conditions to predict non-ideal reactor performance. Tubular reactor performance is nonideal when the mass transfer Peclet number is small enough such that interpellet axial dispersion cannot be neglected. The objectives of this section are to understand the correlations for effective axial dispersion coefficients in packed beds and porous media and calculate the mass transfer Peclet number based on axial dispersion. Before one can make predictions about the ideal vs. non-ideal performance of tubular reactors, steady-state mass balances with and without axial dispersion must be solved and the reactant concentration profiles from both solutions must be compared. If the difference between these profiles with and without interpellet axial dispersion is indistinguishable, then the reactor operates ideally. 

The following strategy should be used to calculate the interpellet axial dispersion coefficient and the mass transfer Peclet number in packed catalytic tubular reactors (see Dullien, 1992, Chap. 6). Initially, one should calculate a simplified mass transfer Peclet number (i.e., Pesimpie) based on the equivalent diameter of the catalytic pellets, equivalent, the average interstitial fluid velocity through the packed bed, (Uj>intetstitiai, and the ordinary molecular diffusion coefficient of reactant A, a, ordinary-... 

Step 19. Determine the coefficient of the axial concentration gradient in the two coupled ODEs that must be solved to calculate the outlet conversion in a packed catalytic tubular reactor with convection, axial dispersion, and chemical reaction. 

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