Abstract

An alternative route towards COx-free production of hydrogen is the thermal catalytic decomposition of methane. In addition to hydrogen, valuable carbon nanomaterials can be formed. Carbon nanofiber formation from methane decomposition over carbon supported NiCu catalysts was studied in-situ using a Thermogravimetric analyzer. We especially investigated how the carbon yield is influenced by reaction parameters. Based on experiments with varying temperature (450–600 °C), two distinct temperature regimes were identified. Different kinetic parameters were derived for the two regimes. Activation energies of 86 and 45 kJ/mol, and reaction orders in methane of close to 1 and 1.5, were found in the low and high temperature regimes, respectively. We postulate that at lower temperature the methane dissociation is rate limiting, while at higher temperature the carbon formation plays a more critical role. At low temperatures mostly full fishbone fibers are formed, whereas at higher temperatures mainly hollow fibers are formed. The maximum carbon yield is obtained at the transition between the two regimes, when the carbon supply and carbon nanostructure formation are balanced.

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