The effect of pore structure on fluid‐solid reactions: Application to the SO2‐lime reaction

The effect of varying pore structures on the kinetics of fluid‐solid reactions is investigated through the random pore model developed in prior papers (Bhatia and Perlmutter, 1980, 1981). By considering several idealized pore‐size distributions it is shown that a solid having a uniform pore size is intrinsically less reactive than one possessing a pore‐size distribution. For solids with bimodal pore size distributions optimal structures are shown to exist for which the reactivity is a maximum. Numerical solutions were obtained to the model equations for various values of the parameters characterizing the pore structure, the diffusion, and the chemical kinetics. The results show that the conversion‐time behavior and the expected ultimate conversion can be very sensitive to variations in surface area and porosity for reactions accompanied by an increase in volume of the solid phase. These findings are in agreement with experimental literature on the SO2‐lime reaction (Ulerich et al., 1978; Borgwardt and Harvey, 1972; Potter, 1969; Falkenberry and Slack, 1968) and the model is shown to fit the data of Borgwardt (1970), and of Hartman and Coughlin (1974, 1976). It is seen that this reaction is diffusion controlled under the conditions of Hartman and Coughlin, in consonance with their own finding using the grain model, and a prior Pigford and Sliger (1973) interpretation. The temperature behavior of the diffusion coefficient in the product layer suggests the participation of an activated process, possibly a solid state diffusion step.