Simulation of packed-bed chromatography utilizing high-resolution flow fields: comparison with models.

A computer simulation of a section of the interior region of a liquid chromatographic column is performed. The detailed fluid flow profile is provided from a microscopic calculation of low Reynolds number flow through a random packed bed of nonporous spherical particles. The fluid mechanical calculations are performed on a parallel processor computer utilizing the lattice Boltzmann technique. Convection, diffusion, and retention in this flow field are calculated using a stochastic-based algorithm. This computational scheme provides for the ability to reproduce the essential dynamics of the chromatographic process from the fundamental considerations of particle geometry, particle size, flow velocity, solute diffusion coefficient, and solute retention parameters when retention is utilized. The simulation data are fit to semiempirical models. The best agreement is found for the "coupling" model of Giddings and the four-parameter Knox model. These models are verified over a wide range of particle sizes and flow velocities at both low and high velocity. The simulations appear to capture the essential dynamics of the chromatographic flow process for non-dimensional flow velocities (Péclet number) less than 500. Since the same packing geometry is utilized for different particle size studies, the interpretation of the parameter estimates from these models can be extended to the physical column model. The simulations reported here agree very well with a number of experiments reported previously.