Hydrocarbon pyrolysis with a methane focus: A review on the catalytic effect and the coke production

• Review on hydrocarbon pyrolysis experiments and modeling.
• Exploration on the catalicity and its influent parameters.
• Temperature, pressure, residence time or S/V ratio are of importance.
• Survey on the associated coke production: characteristics and mechanism.
• Influence of the nature of the reactor: enhancement or limitation of its production.

Hydrocarbon pyrolysis has been widely studied since the 1900s for applications in aerospace as a fuel and/or coolant or for use with fuel cells and hydrogen production with a catalyst. In this context, the role of heterogeneous reactions with homogeneous phase chemistry is unclear despite the fact that it is obviously at the heart of coupled physico-chemical phenomena. In addition, the thermal formation of solid carbon particles – coke, which can be deposited on the structure, impacts the heterogeneous reactions. The aim of this work is to review the available literature on hydrocarbon pyrolysis involving reactions with solid surfaces and coke particles. The influent parameters such as the nature of the fluid, the temperature (up to 2000 K), the pressure (up to 100 bars), the residence time (μs order to min order), the reactor type (plug flow, batch, and perfectly stirred reactor) and the type of catalyst (metallic or more complex such as zeolites) are discussed. Then, a link between catalicity and coke production is addressed. This literature survey focuses in particular on methane because of the growing interest regarding the potential for hypersonic applications.