Modified Energy Span Analysis of Catalytic Parallel Pathways and Selectivity | AIChE

Modified Energy Span Analysis of Catalytic Parallel Pathways and Selectivity

TitleModified Energy Span Analysis of Catalytic Parallel Pathways and Selectivity
Publication TypeJournal Article
Year of Publication2022
AuthorsCohen, M, Vlachos, DG
JournalIndustrial & Engineering Chemistry Research
Volume62
Pagination2191-2201
Date Publishedapr
Keywords9.5, BP6Q5
Abstract

Mechanistic modeling provides vital insights into catalytic reactions. To analyze complex reaction networks with parallel pathways, we leverage the graph theory approach of the Energy Span Model (ESM) to develop a modified energy span analysis (MESA). A new method of cycle plots is proposed to perform reaction pathways analysis visually. We demonstrate this method on two published models: one describing carbon monoxide oxidation and the other simulating ethylene conversion to propanal via hydroformylation or ethane via hydrogenation. Fundamental insights explain kinetic observables, such as a reactant’s negative reaction order. General principles are revealed, such as rate-determining surface species being outside the primary reaction flux cycle and pathway selectivity being a purely kinetic property when reaction conditions are not near equilibrium. Finally, we demonstrate MESA’s consistency with published microkinetic modeling results, highlighting this technique’s extension of the ESM to heterogeneous catalysts using collision theory to describe adsorption steps and concentration effects.

URLhttps://pubs.acs.org/doi/10.1021/acs.iecr.2c01991
DOI10.1021/acs.iecr.2c01991