Pyrolysis of methane is a carbon-economic method to obtain valuable carbon materials and COx- free H2, under the carbon peaking and carbon neutrality goals. In this work, we propose a methane pyrolysis process to produce graphite and H2 using bubble column reactor containing NiO/Al2O3 and NaCl–KCl (molten salt). The process was optimized by the different amounts of NaCl–KCl, the CH4/ Ar ratio and temperature, indicating that the CH4 conversation rate could reach 92% at 900 °C. Meanwhile, we found that the addition of molten salt could obtain pure carbon materials, even if the conversation rate of CH4 decreases. The analysis of the carbon products revealed that graphite could be obtained.

Like bamboo-sprouts after rains, numerous subμm-sized pyrocarbon whiskers growth on the Mullite (3Al2O3·2H2O) substrate could be observed through a looking glass during methane pyrolysis at the temperature of 1050℃ in this study. If the surface of substrate would be scrubbed strongly with iron metals, then finely sticked iron particles were more effective catalytic for nm-sized whisker growth. Numerous fine flakes of pyrolytic carbon were hanging by invisible nm-whiskers as like as small spiders hanging by a spiderweb. This is the identification of nm-sized whisker growth. Therefore if the pyrolysis would be stopped at the initial stage of the whisker growth, the primary lengthening growth was nm-sized whisker. So could we vary arbitrarily sizes of whisker from nm- to μm-sizes. But μm- and nm-whiskers grown with the different growth mechanism; the former was straight and the latter has twigs, The lengthening growth of whisker was depended on the flow pattern pyrolysis species on the active sites of substrate and on the growth duration. We could obtained straight whisker length of 10~20 μm/min during the primary growth and laboratory spiral whisker of 30~40 μm-diameter/hr during the secondary growth.