Fixed-Bed Reactor for Catalytic Hydrocarbon Oxidation

In this example, a process of industrial importance is discussed, that is, partial oxidation of o-xylene in air to phthalic anhydrid (PA) in a multitube fixed-bed reactor. The total production of PA is currently about 7 million lb/year, and almost all of the PA is manufactured by the multitube fixed-bed process [1],[2]. In this process, the temperature is usually kept between 400-475oC, while the residence time varies between 0.5-5 seconds. The catalyst of choice is usually a mix of vanadium oxide and potassium sulfate on a silica support. The most important factor to consider for this process is the temperature throughout the reactor. The reactions taking place in the reactor are highly exothermic, and in order to eliminate runaway conditions, the reactor needs to be cooled. The temperature distribution will, in turn, affect the yield of the phthalic anhydride, which is to be maximized. We can control the temperature distribution by varying tube diameter, residence time, wall temperature (cooling rate), as well as the inlet temperature of the feed. In this example we will cover some of these factors by setting up a detailed model of the system using the so-called two-dimensional pseudo homogeneous model as described in the literature [2], [3], [4]. Most of the time, tubular reactors are modeled with the assumption that concentration and temperature gradients only occur in the axial direction. The only transport mechanism operating in this direction is the overall flow itself, which is considered to be of plug-flow type, that is, all the fluid elements are assumed to move with a uniform velocity along parallel streamlines. In this example, we will take a more general approach, and we will account for variations of the concentrations and the temperature in the axial direction. We will also account for mixing in the axial direction, which is due to turbulence and the presence of packing. The axial mixing is described by means of effective diffusivities and conductivities.

Model Definition
We will investigate this system by first setting up a model in 2D, where we assume that we have rotational symmetry. We will then introduce a few approximations, and show that this problem can be described, to a satisfactory extent, by a time-dependent 1D model. The obvious advantage with the latter approach is the much lower memory requirement. However, it has a few limitations, one of which is that it is restricted to simulate steady-state behavior. Furthermore, in cases where you cannot neglect axial mixing, a full 2D model is required to obtain accurate results. The reaction kinetics of this process is of a rather complex nature but can, to a satisfactory extent, be explained by the following scheme [2], [3], [4]:

Figure 1: Reaction paths. A represents o-xylene, B phthalic anhydride, and C is the total amount of carbon monoxide and carbon dioxide. Due to a very high excess of oxygen, the reactions can be considered to be pseudo-first-order, and we can then describe the reactions kinetics as follows:

Where y0 represents the mole fraction of oxygen, and yA0 is the inlet mole fraction of oxylene. Furthermore, xA is the total conversion of o-xylene, xB is the conversion of oxylene into phthalic anhydride, and xC represents the total conversion into carbon monoxide and carbon dioxide. The rate coefficients depend on temperature as described by the Arrhenius law according to the following expressions:

Where T0 is the inlet temperature of the reactor, and T = T- T0.

AXISYMMETRIC 2D MODEL
A schematic description of the reactor is given in Figure 2. The convective flow of gas takes place from the bottom to top and axisymmetry is assumed, which reduces the 3D geometry to two dimensions.

Figure 2: Schematic representation of the reactor. The design equations for this system can be described by [3], [4]:

Where us is the superficial velocity, g is the gas density, b is the catalyst bulk density, ctot the total concentration, yA0 the inlet mole fraction of o-xylene, and eff the effective thermal conductivity of the bed. We will now make use of the fact that xA = xB + xC, which means that we only need to solve for two mass balances, resulting in the following design equations:

The rate equations can be rewritten accordingly:

The boundary conditions for this system are as follows; see Figure 2 above for reference:

At the outlet of the reactor, we will assume that the convective part of the mass and heat transport vector is dominating. Due to the large aspect ratio of our model geometry, we are going to scale our equations. In this case, the reactor is about 200 times its radial dimension, more specifically, 3 meter long and 0.0127 meter in radius. By scaling the equations, we avoid excessive number of elements and node points when setting up the mesh. The new scaled r and z-coordinates, and the new differentials for the mass balances, can be written as

In the mass balances, c is differentiated twice in the diffusion term, which implies that the z-component of diffusion in the mass balance has to be multiplied by (1 /scalez)2 and by (1 /scaler)2 for the r-component. The convective part is only differentiated once, and has to be multiplied by (1 /scalez). The scaling of the diffusive part of the flux can be introduced as an anisotropic diffusion coefficient. This gives the diffusion coefficient according to the matrix below:

Similarly for the heat balance, we get thermal conductivity according to the following matrix:

Results
The default plot shows the conversion of o-xylene to phthalic anhydride.

Figure 3: Temperature distribution across the tubular half plane A plot of the temperature, see Figure 3 above, reveals that the temperature goes through a maximum not far from the reactor inlet. This so-called hotspot is a quite common phenomenon for a system with exothermic reactions to which cooling is applied. Also, note that the radial temperature gradients are quite significant around this hotspot. Figure 4 shows the composition and temperature distribution in the reactor in the axial direction. The figure shows the bulk mean conversions and the temperature profile for an inlet temperature of 354 o C. We can see that the phthalic anhydride conversion falls off somewhat along the tube (middle line), which is typical for consecutive reactions. Furthermore, it can be seen that the temperature goes through a maximum, a so-called hotspot, at Tm equal to about 30 oC, not far from the inlet of the reactor.

Figure 4: Composition and temperature versus axial coordinate in the reactor.

Figure 5: Temperature versus radial coordinate in the reactor. In Figure 5, we can see that the radial temperature gradients are quite severe, as the temperature along the symmetry axis is well above the mean temperature. Based on this information, we can draw the conclusion that a one-dimensional model with axial mixing would not be good enough to describe this system

Figure 6: Average dimensionless temperature vs. axial coordinate for different inlet temperatures

The parameter study of the inlet temperature gives Figure 6 for the average temperature in the axial direction. From this figure, we can see that the inlet temperature of the tubular reactor does affect the axial temperature quite dramatically. A high temperature increases the production rate of phthalic anhydride, but it may also increase the production of carbon monoxide and carbon dioxide. Furthermore, too high a temperature may be detrimental to the catalyst, which means that it is very important to have good control of the feed temperature of the reactor. It should also be mentioned in this context that the results in this model are in excellent agreement with the model by Froment [1]. Froments model was done in 1967 and 2D simulations were not possible for a complex model like this. This also implied that these models were limited to steady state simulations. The model presented in the first section can be easily rewritten to a time-dependent form for use in automatic control and start-up simulations.

References
[1] G. F. Fro ment, Fixed Bed Catalyt ic Reactors, Ind. Eng. Chem., 59(2), 18, 1967 [2] SRI Internat ional Consult ing, http://pep.sric.sri.com/, 2001 [3] G. F. Froment and K. B. Bischo ff, Chemical Reactor Analysis and Design, John Wiley & Sons, 1990 [4] C. N. Saterfield, Heterogeneous Catalysis in Industrial Pract ice, Mc Graw-Hill, 1991

Model Library Chemical_Engineering_Module/Reaction_Engineering/ fixed_bed_reactor_exo

Modeling Using the Graphical User Interface

1. Start FEMLAB 2. In the Model Navigator, click the Multiphysics button, and set the Space dimension list to Axial Symmetry (2D). 3. Highlight the application mode Chemical Engineering Module/Mass balance/Convection and Diffusion. Enter Dependent variables: xb xc (space separated), and Application mode name: massbal. 4. Click the Add button.

5. Select the application mode Chemical Engineering Module/Energy balance/Convection and Conduction. Name the application mode energybal and leave the dependent variables to the default T. Click Add. 6. Highlight the Convection and Diffusion application mode in the Multiphysics list on the right hand of the pane.

7. Click the Application Mode Properties button. Switch the Equation form to Conservative. Click OK

8. Repeat the procedure to set the conservative equation form for the Convection and Conduction application mode. 9. Click OK in the Model Navigator.

OPTIONS AND SETTINGS

1. Define the following constants in the Options/Constants dialog box: NAME EXPRESSION Deff 3.19e-7 us rhob rhog lambda cp ctot alpha T0 deltaH1 deltaH3 ya0 y0 B1 B2 B3 1.064e-3 1300 1293 0.78e-3 0.992 44.85 0.156 627 -1.285e6 -4.564e6 0.00924 0.208 13588 15803 14394

2. Define the following Expressions dialog box:

expressions

in

the

Options/Expressions/Scalar

NAME scaler scalez A1 A2 A3 k1 k2 k3 rb rc

EXPRESSION 0.0127/1 3/5 exp(19.837)/3600 exp(20.86)/3600 exp(18.97)/3600 A1*exp(-B1/(T+T0)) A2*exp(-B2/(T+T0)) A3*exp(-B3/(T+T0)) ya0*y0*(k1*(1-xb-xc)-k2*xb) ya0*y0*(k2*xb+k3*(1-xb-xc))

GEOMETRY MODELING
1. Click the Rectangle/Square button on the Draw toolbar and draw a rectangle of arbitrary dimension. Double-click on the rectangle and type the values listed below in the corresponding edit fields. EDIT FIELD VALUE Width 1 Height r: z: 5 0 0

2. Click the Zoom Extents button on the Main toolbar.

PHYSICS SETTINGS
Boundary Conditions
1. Select 1 Convection and Diffusion (massbal) from the Multiphysics menu.

10

2. Open the Physics/Boundary Settings dialog box. 3. Enter the boundary conditions according to the following table: BOUNDARY 1,4 2 3 Type Insulation/Symmetry Concentration Convective flux xb0, xc0 0

NOTE: Make sure that you specify the boundary conditions both on the xb and xc tabs.

Subdomain Settings
1. Open the Physics/Subdomain Settings dialog box, and select subdomain 1. 2. Start with the xb tab. Click the D anisotropic radio button. Place the cursor in the edit field next to this button and the diffusivity matrix will appear. Type Deff/scaler^2 in the r-diffusivity field (upper left) and Deff/scalez^2 in the zdiffusivity field (lower right).

11

1. Repeat this procedure on the xc tab. The table below summarizes the complete subdomain settings: SPECIES XB D (r-direction) Deff/scaler^2 D (z-direction) Deff/scalez^2 R u v 0 us/scalez XC Deff/scaler^2 Deff/scalez^2 0 us/scalez

rb*rhob/ctot/ya0 rc*rhob/ctot/ya0

2. Click the Artificial Stabilization button, check the middle check box (Streamline diffusion ) with default parameters. Click OK. 3. Click OK in the Subdomain Settings dialog box.

12

Boundary Conditions
1. Select 2 Convection and conduction (energybal) from the Multiphysics menu. 2. Enter the boundary conditions according to the following table: BOUNDARY 1 2 3 4 Type Thermal insulation Temperature Convective flux Heat Flux q0 T0 0 -alpha*T/scaler

Subdomain Settings
3. Open the Physics/Subdomain Settings dialog box, and select subdomain 1. 4. Click Physics tab. Click the k anisotropic radio button. Place the cursor in the edit field next to this button and the thermal conductivity matrix will appear. Type lambda/scaler^2 in the r-diffusivity field (upper left) and lambda/scalez^2 in the z-diffusivity field (lower right). 5. The table below summarizes the complete subdomain settings:

13

SUBDOMAIN 1 k (r-direction) lambda/scaler^2 k (z-direction) lambda/scalez^2 Cp Q u v rhog cp rhob*((-deltaH1)*rb+(-deltaH3)*rc) 0 us/scalez

MESH GENERATION
1. Initialize the mesh. 2. Refine the mesh once.

COMPUTING THE SOLUTION

Solve the problem by clicking the Solve button.

POST PROCESSING
1. Click the Plot Parameters button and go to the Surface tab. 2. Select Temperature from the Expression list.

PARAMETRIC STUDY
1. Click the Solver Parameters button and select Solver: Parametric nonlinear. 2. Go to Parameter area, and enter the following: EDIT FIELD Name of parameter VALUE T0

List of parameter values 625 626 627 628 629 3. Click OK. 4. Solve the parameterized problem by clicking the Solve Problem button.

14

15