Top‐down kinetic modeling from power law to elementary steps using KASTER: A methane steam reforming case study

Abstract

AbstractA top‐down methodology for kinetic model construction including regression against experimental data is proposed using “KASTER.” As a case study, it is applied in the assessment of methane steam reforming (MSR) including water–gas shift (WGS) on a Ni catalyst at 923 K. The degree of detail in the reaction mechanism and the corresponding model is gradually enhanced, typically ranging from a simple power law to a microkinetic model. The reactor equations are solved transiently, preventing the numerical challenges encountered in the steady‐state solution, particularly for microkinetic models. The microkinetic variant indicated that CH4 dissociative adsorption and CO formation are kinetically relevant steps in MSR, while COOH formation is rate‐determining in WGS. However, the model providing the best balance between detail accounted for and parameter significance corresponded to a Langmuir–Hinshelwood–Hougen–Watson (LHHW) mechanism accounting for dissociative adsorption, with CO formation and COOH formation as rate‐determining steps for MSR and WGS, respectively.