title: A systematic investigation of algorithm impact in preparative chromatography with experimental verifications.
abstract: Computer-assisted optimization of chromatographic separations requires finding the numerical solution of the Equilibrium-Dispersive (ED) mass balance equation. Furthermore, the competitive adsorption isotherms needed for optimization are often estimated numerically using the inverse method that also solves the ED equations. This means that the accuracy of the estimated adsorption isotherm parameters explicitly depends on the numerical accuracy of the algorithm that is used to solve the ED equations. The fast and commonly used algorithm for this purpose, the Rouchon Finite Difference (RFD) algorithm, has often been reported not to be able to accurately solve the ED equations for all practical preparative experimental conditions, but its limitations has never been completely and systematically investigated. In this study, we thoroughly investigate three different algorithms used to solve the ED equations: the RFD algorithm, the Orthogonal Collocation on Finite Elements (OCFE) method and a Central Difference Method (CDM) algorithm, both for increased theoretical understanding and for real cases of industrial interest. We identified discrepancies between the conventional RFD algorithm and the more accurate OCFE and CDM algorithms for several conditions, such as low efficiency, increasing number of simulated components and components present at different concentrations. Given high enough efficiency, we experimentally demonstrate good prediction of experimental data of a quaternary separation problem using either algorithm, but better prediction using OCFE/CDM for a binary low efficiency separation problem or separations when the compounds have different efficiency. Our conclusion is to use the RFD algorithm with caution when such conditions are present and that the rule of thumb that the number of theoretical plates should be greater than 1000 for application of the RFD algorithm is underestimated in many cases.
authors.affiliation: Analytical Chemistry, Department of Chemistry and Biomedical Sciences, Karlstad University, SE-651 88 Karlstad, Sweden.
authors.forename: Martin
authors.initials: M
authors.lastname: Enmark
authors.forename: Robert
authors.initials: R
authors.lastname: Arnell
authors.forename: Patrik
authors.initials: P
authors.lastname: Forssén
authors.forename: Jörgen
authors.initials: J
authors.lastname: Samuelsson
authors.forename: Krzysztof
authors.initials: K
authors.lastname: Kaczmarski
authors.forename: Torgny
authors.initials: T
authors.lastname: Fornstedt
mesh_terms: D000465:Algorithms; D002853:Chromatography, Liquid / Q000379:methods*; D020342:Finite Element Analysis; D008956:Models, Chemical; D015203:Reproducibility of Results