Carbon black and hydrogen production from methane pyrolysis: measured and modeled insights from integrated gas and particle diagnostics in shock tubes

Abstract

Methane (CH4) pyrolysis is a promising route to co-produce hydrogen (H2) and carbon black (CB) while avoiding emissions associated with steam-methane reforming and furnace black processes. Model development of pyrolytic CB synthesis requires experimental observations of concurrent gas chemistry, particulate formation, and morphology. This work presents a combined experimental and modeling study of CH4 pyrolysis behind reflected shock waves in 5% CH4/Argon mixtures at post-reflected shock temperatures (T5) of 1850-2450 K and P5 around 4.5 atm. Laser absorption diagnostics quantified CH4, C2H4, and C2H2 mole fractions, while multiwavelength extinction (633 and 1064 nm) resolved time-dependent particle formation and the temperature-dependent evolution of optical maturity. Simulations reproduce small-molecule speciation well, but large variations in predicted polycyclic aromatic hydrocarbons (PAHs) persist among models. Coupled gas-particle simulations capture accurate volume fraction (fv) trends and the influence of gas dynamics but underpredict induction times at high T5. Samples collected at the shock tube endwall were analyzed by transmission electron microscopy (TEM) to quantify primary particle size distributions and nanostructure arrangement. Image segmentation and manual measurements showed reduced primary particle size growth (dp) with increasing T5, while graphitic nanostructure generally increased. This study provides an integrated benchmark for improving models of CB and H2 production from CH4 pyrolysis by constraining gas-phase kinetics, PAH-driven inception, particle dynamics, and particle maturity. The results highlight that accurate partitioning of mass between particle number and particle size is an important constraint for further model development.