Microkinetic insights into the impact of coking in dry reforming of methane

Abstract

Coking remains one of the most critical challenges in dry reforming of methane (DRM), causing catalyst deactivation and severe performance loss. While microkinetic modeling (MKM) can capture reaction dynamics at the elementary-step level, existing DRM models lack the ability to represent the evolving nature of coke formation and its mechanistic impact on the reaction network. This study introduces a novel coke-inclusive MKM that explicitly incorporates coke formation pathways and is experimentally validated against DRM data. To interpret the complex, time-dependent behavior of coking, we develop a novel phase-based framework that systematically segments coke accumulation into distinct temporal regimes, each characterized by unique rates and patterns of carbon buildup. Phase-specific mechanistic analysis reveals a gradual shift in the dominant reaction pathways as coking progresses. Early-stage coke formation involves a broad set of surface reactions, opening multiple opportunities for targeted intervention, whereas later stages show a concentration of coking influence in a few critical reactions, such as methane decomposition and CO₂ adsorption. To enhance practicality, a reduced-order coke-inclusive MKM is constructed, retaining essential kinetic features while greatly improving computational efficiency. This integrated modeling strategy — the first to combine a coke-inclusive MKM with phase-based analysis — provides a powerful bridge between detailed reaction mechanisms and application-focused catalyst and reactor design, offering new tools to improve catalyst durability and advance the sustainability of DRM systems.