Effective thermal conductivity inside catalyst pellets

When a fast reaction is highly exothermic or endothermic and, additionally, the effective thermal conductivity of the catalyst is poor, then significant temperature gradients across the pellet are likely to occur. In this case the mass balance (eq 32) and the enthalpy balance (eq 33) must be simultaneously solved using the corresponding boundary conditions (eqs 34-37), to obtain the concentration profile of the reactant and the temperature profile inside the catalyst pellet. The exponential dependence of the reaction rate on the temperature thereby imposes a nonlinear character on the differential equations which rules out an exact analytical treatment. Approximate analytical solutions [83, 99] as well as numerical solutions [13, 100, 110] of eqs 32-37 have been reported by various authors. 

In the general case where the active material is dispersed through the pellet and the catalyst is porous, internal diffusion of the species within the pores of the pellet must be included. In fact, for many cases diffusion through catalyst pores represents the main resistance to mass transfer. Therefore, the concentration and temperature profiles inside the catalyst particles are usually not flat and the reaction rates in the solid phase are not constant. As there is a continuous variation in concentration and temperature inside the pellet, differential conservation equations are required to describe the concentration and temperature profiles. These profiles are used with intrinsic rate equations to integrate through the pellet and to obtain the overall rate of reaction for the pellet. The differential equations for the catalyst pellet are two point boundary value differential equations and besides the intrinsic kinetics they require the effective diffusivity and thermal conductivity of the porous pellet. 

Catalyst supports such as silica and alumina have low thermal conductivities so that temperature gradients within catalyst particles are likely in all but the finely ground powders used for infrinsic kinetic studies. There may also be a film resisfance fo heaf fransfer af fhe exfemal surface of the catalyst. Thus the internal temperatures in a catalyst pellet may be substantially different than the bulk gas temperature. The definition of the effectiveness factor, Equation 10.23, is unchanged, but an exothermic reaction can have reaction rates inside the pellet that are higher than would be predicted using the bulk gas temperature. In the absence of a diffusion limitation, rj > 1 would be expected for an exothermic reaction. (The case > 1 is also possible for some isothermal reactions with weird kinetics.) Mass transfer limitations may have a larger... 

---