Pore and surface diffusion in multicomponent adsorption and liquid chromatography systems

• Published in: AIChE journal 1996-05, Vol.42 (5), p.1244-1262
• Main Authors: Ma, Z., Whitley, R. D., Wang, N.-H. L.
• Format: Article
• Language: English
• Subjects: Adsorption; Applied sciences; Chemical engineering; Exact sciences and technology
• ISSN: 0001-1541; 1547-5905
• DOI: 10.1002/aic.690420507

A generalized parallel pore and surface diffusion model for multicomponent adsorption and liquid chromatography is formulated and solved numerically. Analytical solution for first‐ and second‐order central moments for a pulse on a plateau input is used as benchmarks for the numerical solutions. Theoretical predictions are compared with experimental data for two systems: ion‐exchange of strontium, sodium, and calcium in a zeolite and competitive adsorption of two organics on activated carbon. In a linear isotherm region of single‐component systems, both surface and pore diffusion cause symmetric spreading in breakthrough curves. In a highly nonlinear isotherm region, however, surface diffusion causes pronounced tailing in breakthrough curves; the larger the step change in concentration, the more pronounced tailing, in contrast to relatively symmetric breakthroughs due to pore diffusion. If only a single diffusion mechanism is assumed in analyzing the data of parallel diffusion systems, a concentration‐dependent apparent surface diffusivity or pore diffusivity results; for a convex isotherm, the apparent surface diffusivity increases, whereas the apparent pore diffusivity decreases with increasing concentration. For a multicomponent nonlinear system, elution order can change if pore diffusion dominates for a low‐affinity solute, whereas surface diffusion dominates for a high‐affinity solute.