Global ETD Search

Return to search

Catalyst Deactivation in Chemical and Biochemical Systems

Catalyst deactivation in single catalyst pellets and in an isothermal catalytic fixed bed reactor have been analytically studied. The work reported here is unlike the vast majority of previous theoretical analyses which are numerical. This thesis deals with two types of deactivation - parallel and series mechanisms in which respectively, reactant and product are directly responsible for poisoning. For the single particle studies, the principal analytical tools used are based on singular perturbation theory. Use of these techniques in the temporal domain depends crucially on the smallness of the ratio of the deactivation rate constant to that of the main reaction. Depending on the range of Thiele modulus, whether small, intermediate or large, three different techniques are used in the spatial domain. First, when the Thiele modulus is small, a lumping technique due to Frank-Kamentskii (1955) is used to replace the Laplacian operator by a suitable constant. This reduces the coupled partial differential equations to ordinary ones. Main chemical kinetics of n-th order and of Michaelis-Menten type are investigated. Second, when the Thiele modulus is very large, matched asymptotic expansions in the spatial domain are used. The analysis is based on the smallness of the inverse Thiele modulus, 1/phi2. A moving reaction zone of thickness 0(1/phi) is found to separate the dead shell from the active core of the catalyst pellet. The catalyst activity profile exhibits a sharp change within the reaction zone and the structure of this profile is found to be self-preserving during the period of its propagation. Solutions are obtained for three different geometries - planar, cylindrical and spherical. The large Thiele modulus results obtained here are found to be more accurate than the shell-model solutions of Masamune and Smith (1966) (except for a slab geometry, when they are identical). Finally, for an intermediate range of Thiele modulus, finite Sturm-Liouville integral transforms along with the concept of an effective average are successfully applied. The approach taken is novel, and although not rigorously justifiable, it leads to results of suprising accuracy. The versatility of the technique is demonstrated by application to various non-linear problems which posess exact solutions and remarkable agreement is found. The finite-cylindrical catalyst pellet is also investigated using a double-integral transform in the spatial domain and it is shown that for small Thiele modulus, the infinite cylinder and slab results are good approximations to finite length cylinders with small and large ratio, R/L, respectively. The analytical solutions reported in this thesis agree well with the known numerical results of others (Masamune and Smith, 1966; Khang and Levenspiel, 1973 and Lamba and Dudukovic, 1978). The parametric - dependence of these solutions is explicit and numerical results can be easily obtained from them by hand calculation. All the single pellet results are brought together in the final chapter and used to analyze the performance of isothermal fixed-bed reactors undergoing poisoning. Such effects as external mass transfer resistance, pellet shape and chemical kinetic type are included in the analysis, which embraces the entire range of Thiele modulus.