Excerpt from the Proceedings of the 2006 Nordic COMSOL Conference

Modeling of Heat and Mass Transport in a Nonlinear Catalytic Bed Reactor

A. Machac1, R. Henda *,2 and B. Nilsson2 1 School of Engineering, Laurentian University, Sudbury, ON P3E 3C7, Canada, 2Department of Chemical Engineering, Lund University, PO Box 124, SE-221 00 Lund, Sweden
*Corresponding author: School of Engineering, Laurentian University, Sudbury, ON P3E 3C7, Canada, rhenda@laurentian.ca

Abstract: Heat and mass transport phenomena in a tubular catalytic bed reactor are numerically investigated. A two-dimensional pseudoheterogeneous model, accounting for transport in the solid and fluid phases, with axial and radial dispersions is used to describe the reactor. The reactor model takes the form of a set of coupled nonlinear partial and ordinary differential equations. Different process parameters related to heat and mass exchange in the catalyst bed are defined. The solution of the model yields the distributions of temperature and concentration in the reactor. The calculation results show the development of a hot spot in the reactor. The effects of inlet process conditions are investigated and their impact on the behavior of the reactor is analyzed. Keywords: Nonlinear catalytic bed, Heat transport, Mass transport, Exothermic reaction, Tubular reactor.

function of temperature. If no cooling is applied to the reactor, the temperature will increase very rapidly along the reactor, potentially damaging both the catalyst and reactor. This undesirable phenomenon is referred to as hot spot [8, 9]. Selectivity of the process may also be deteriorated through the initiation of undesired side chemical reactions. This study aims at investigating heat and mass transport in a two-dimensional tubular catalytic bed reactor, where an exothermic chemical reaction takes place, using numerical modeling. The effects of the process conditions at the reactor inlet are are numerically investigated and their impact on the dynamic behavior of the system in question is analyzed.

2. Reactor Model and Formulation

A simple cross-sectional view of the reactor system is illustrated in Figure 1.
Outlet z

1. Introduction
Chemical reactors where strong couplings exist between various transport phenomena and with chemical reaction kinetics are very common in modern chemical process industries such as powder technology, catalysis, and biotechnology, to name just a few. These systems are strongly non-linear due to the nature of reaction kinetics and internal feedback between the various chemical and physical phenomena, and as such present a rich variety of non-trivial behaviors, e.g., oscillations, multiple steady-states, hot spots, etc [1-7]. Since most chemical processes involve some kind of energy exchange within their midst, heat effects further add to the nonlinear nature of the processes and to the palette of complex process behavior. Such is the case of catalytic bed reactors with exothermic chemical reactions, e.g., oxidation and hydrogenation. The rate of the chemical reaction is generally a complex exponential

Wall

Wall Rt

Cooling jacket r

Inlet s f

Figure 1: Simplified schematics of the catalytic bed reactor

Excerpt from the Proceedings of the 2006 Nordic COMSOL Conference

The system consists of a packed bed of catalyst (s: solid phase) and gaseous reactants (f: fluid phase). The reactor tube is placed in a cooling jacket. In the present work, we consider the well documented exothermic oxidation reaction of carbon monoxide, CO, into carbon dioxide, CO2, over copper chromite as the catalyst [9] (see the Appendix). The two-dimensional reactor is described via two partial differential equations (PDEs), accounting for the mass and energy balances in the fluid phase, and two ordinary differential equations (ODEs), accounting for the mass and energy balances in the solid phase. The transport equations in dimensionless form are given by the following pseudo-heterogeneous model Mass balance: Fluid phase:
a
C f t = 1 2C f Pem, a z 2 + C f 1 1 r Pem, r r r r +

where Cf and Cs are the dimensionless concentrations of carbon monoxide in the fluid and solid phases, respectively, and f, and s are the dimensionless temperatures of the fluid and solid phases, respectively. The independent variables are the dimensionless time, t, and dimensionless radial, r, and axial, z, coordinates. For the definition of the dimensionless reaction rate, R, see the Appendix. Equations 1-4 are subject to the following initial and boundary conditions: IC: t = 0, Cf = 0, Cs = 0, f = 0, s = 0. BCs: z = 0, r,

C f z

= Pe m,a (C f C in ) ,

f z

= Pe h ,a ( f in ) (5) C f z f z =0

z = L/Rt, r,

=0, f z f z

=0

C f z

+ St m C s C f

(1)

r = 0, z,
Solid Phase:

C f z C f z

=0,

(1 ) a

Cs

= (1 ) Da R Cs , s + t

r =1, z,
(2)

=0,

= Bi ( f w )

St m C s C f
Energy balance: Fluid phase:
f t 2 f 1 Peh, a z 2 f 1 1 r + Peh, r r r r +

with the following dimensionless variables and parameters

* C* Cs f r = r * , z = z * , t = t * , C f = * , Cs = * , Rt Rt to C in C in * h w Rt * in * * f , s = s * in , Bi = , f = * k r ,eff ad ad * ad = * H r C in

f + St h s f z
Solid Phase:

(3)

f c p, f
u o Rt D r ,eff

,a =

Rt u o Rt , Pe m,a = , to uo D a ,eff u o f c p , f Rt k a ,eff a p h m Rt uo

Pe m,r =

, Pe h,a =

, ,

(1 ) s c p, s
f c p, f

= (1 ) Da R Cs , s + t

Pe h,r =
(4)

u o f c p , f Rt k r ,eff

, St m =
' s Rt

St h s f

St h =

a p h p Rt u o f c p, f

, Da =

* u o C in

(C s , s )

in

Excerpt from the Proceedings of the 2006 Nordic COMSOL Conference

where the asterisk denotes variables with absolute values. The pseudo-heterogeneous model given by Eqs. 1-4, along with the initial and boundary conditions (Eq. 5), has been numerically implemented using Comsol Multiphysics [10]. The latter has provided for the discretization of the PDEs using the method of finite elements and for their solution through an implicit ODE solver, based on the method of lines.

3.2 Simulation Results

3. Results and Discussion

3.1 Model Data

The calculated temperature profile of the fluid phase throughout the catalytic bed reactor is shown in Figure 2. Heat transport is clearly two dimensional as a temperature front (hot spot) develops near the reactor inlet. Figure 3 illustrates the difference in temperature between the solid and fluid phases along the vertical line (r = 0.5) shown in Fig. 2. The temperature difference is quite appreciable and can reach over 20 K near the hot spot region. The value of the hot spot is at maximum near the bed centerline as shown in Fig. 4. The evolution of

The data used for the calculation of the concentration and temperature profiles inside the catalytic bed reactor are listed in Table 1. Materials properties and effective transport parameters have been estimated using a number of widely known correlations. The literature pertinent to this study is provided by [11-15]. The discretization mesh used in the calculations has been refined and the integration time step has been decreased until the calculated concentration and temperature profiles have become independent of both spatial and time discretization steps.
Table 1: Geometry, properties, operating conditions, kinetic and transport parameters used in the simulation.

L Rt

1m 0.02655 m 0.4 0.5 mol/m3 0.1 m/s 385 K 385 K 10.6 kmol/m 31.1 mol/m3 29.45 J/mol/K 149.32 J/mol/K 39.7 kmol/kg/s -23.8 kJ/mol 57.29 kJ/mol
3

o bco ads H co o bo 2 ads H o 2 o bco ads H co Pem,a

6.81 10-8 Pa-1 30.60 kJ/mol 3.08 10-5 Pa-1 24.44 kJ/mol 6.81 10-8 Pa-1 30.60 kJ/mol 2 10 2 8 4.13 1.21 0.24 683

Figure 2. Temperature distribution of the fluid phase in the reactor.

Cin uo
* in
* w s f cpf cps o kr

Pem,r Peh,a Peh,r Sth Sth Bi Re

H r Ea

Figure 3. Temperature difference between the solid and fluid phases at r = 0.5 and t = 1.

Excerpt from the Proceedings of the 2006 Nordic COMSOL Conference

Figure 4. Radial temperature profile of the fluid at z = 2 (hot spot locus) and t = 1.

Figure 6. Concentration of CO as a function of time (increasing in arrow direction) in the reactor at r = 0.5.

temperature of carbon monoxide have been investigated. As the value of Cin is reduced by a factor of five, the magnitude of the hot spot is decreased to just over 13 K relatively to inlet temperature, as shown in Figure 7. The temperature difference between the two phases does not exceed 4 K in this case. A decrease in * in by 20 K does not seem to have a substantial effect on the magnitude of the hot spot. Figure 8 indicates that the value of the hot spot goes down by 10 K in comparison with the results given in Fig. 5. The temperature difference between the

Figure 5. Temperature distribution of the fluid as a function of time (increasing in arrow direction) in the reactor at r = 0.5.

the fluid temperature with time is depicted in Figure 5. As can be noticed, the magnitude of the hot spot increases substantially with time to reach about 75 K relatively to the inlet temperature and under the prevailing process conditions. The temperature of the hot spot is so high that carbon monoxide feed concentration is fully converted downstream the hot spot as shown in Figure 6. In order to assess the sensitivity of the magnitude of the hot spot to process inlet conditions, the effects of feed concentration and

Figure 7. Temperature distribution of the fluid in the reactor for Cin = 0.1 mol/m3 at r = 0.5 and t = 1.

Excerpt from the Proceedings of the 2006 Nordic COMSOL Conference

Figure 8. Temperature distribution of the fluid in the

* reactor for in = 360 K at r = 0.5 and t = 1.

solid and fluid phases is reduced from ~20 K (Fig. 3) to ~14 K.

4. Conclusions
We have investigated heat and mass transport in a wall-cooled catalytic bed reactor using numerical simulations. A pseudo-heterogeneous model, including axial and radial dispersions, has been used to model the transport phenomena along with an exothermic reaction. The results have shown that the model is clearly two dimensional. A hot spot develops near the inlet of the reactor under the process conditions of this study. The findings have indicated that a reduction in carbon monoxide concentration can drastically decrease the value of the hot spot. The effect of the inlet temperature of the fluid on the hot spot is less evident. In prospective work, the effect of transport parameters on the dynamic behavior of the catalytic bed reactor will be analyzed.

5. References
1. Alhumaizi, K., Henda, R. and Soliman, M. Numerical analysis of a reaction-diffusionconvection system. Computers and Chemical Engineering, 27, pp. 579-594 (2003). 2. Chan, S.H. and Hoang, D.L. Chemical reactions in the exhaust system of a cold-start engine. Chemical Engineering Technology, 23, pp. 727-730 (2000).

3. Dekker, N.J.J., Hoorn, J.A.A., Stegenga, S., Kapteijn, F. and Moulijn, J.A. Kinetics of the CO oxidation by O2 and N2O over Cu-Cr/Al2O3. American Institute of Chemical Engineering Journal, 38, pp. 385-396 (1992). 4. Ganesan, P. and Rani, H.P. On diffusion of chemically reactive species in convective flow along a vertical cylinder. Chemical Engineering and Processing, 39, pp. 93-105 (2000). 5. Henda, R. and Alhumaizi, K. Spatiotemporal patterns in a two-dimensional reactiondiffusionconvection system: effect of transport parameters. Mathematical and Computer Modelling, 36, pp. 1361-1373 (2002). 6. Sheintuch, M. and Nekhamkina, O. Pattern formation in homogeneous reactor models. American Institute of Chemical Engineering Journal, 45, pp. 398-409 (1999). 7. Sheintuch, M., Nekhamkina, O.A., Nepomnyashchy, A.A. and Rubinstein, B.Y. Nonlinear analysis of stationary patterns in convection-reaction-diffusion systems. Physical Review, 61, pp. 2436-2444 (2000). 8. Borkink, J.G.H. and Westerterp, K.R. Significance of axial heat dispersion for the description of heat transport in wall-cooled packed beds. Chemical EngineeringTechnology, 15, pp. 371-384 (1992). 9. Koning, G.W. and Westerterp, K.R. Modeling of heat transfer in wall-cooled tubular reactors. Chemical Engineering Science, 54, pp. 25272533 (1999). 10. Comsol AB, Stockholm (Sweden) (2006). 11. Agnew, J.B. and Potter, O.E. Heat transfer properties of packed tubes of small diameter. Transactions of the Institute of Chemical Engineering, 48, pp. 15 (1970). 12. Bauer, R. and Schlunder, E.U. Effective radial thermal conductivity of packings in gas flow. Part I. Convective transport coefficient. Int. Chem. Eng., 18(2), pp. 189204. (1978). 13. Elsari, M. and Hughes, R. Axial effective thermal conductivities of packed beds. Applied Thermal Engineering, 22, pp. 1969-1980 (2002). 14. Incropera, F.P. and DeWitt, D.P. Fundamentals of Heat and Mass transfer, 5th edition, John Wiley, Inc., New York (2002). 15. Klemme, S. and Miltenburg, J.C. van. Thermodynamic properties of nickel chromite (NiCr2O4) based on adiabatic calorimetry at low temperatures. Phys. Chem. Minerals, 29, pp. 663-667 (2002).

Excerpt from the Proceedings of the 2006 Nordic COMSOL Conference

6. Acknowledgements
The principal author (R.H.) acknowledges the financial support of the Center for Chemical Process Design and Control (CPDC) at Lund University (Sweden).

7. Appendix
The reaction rate of carbon monoxide conversion over copper chromite (CO + O2 CO2, Hr) is given by the following expression [9]
(C s , s ) == k r bCO pCO 1 + bCO pCO + bO pO 2 2

where pi (i = CO, O2) is the partial pressure of i, and k r = k ro e Ea / Rg T

, bi = bio e

H iads / R g T

The dimensionless reaction rate is defined by R (C s , ) = (C s , s ) (C s , s ) in

where the denominator term is the reaction rate at inlet conditions.