Although steam methane reforming (CH₄ + 2H₂O → 4H₂ + CO₂) is the most commercialized process for producing hydrogen from methane, more than 10 kg of carbon dioxide is emitted to produce 1 kg of hydrogen. Methane pyrolysis (CH₄ → 2H₂ + C) has attracted much attention as an alternative to steam methane reforming because the co-product of hydrogen is solid carbon. In this study, the simultaneous production of hydrogen and separable solid carbon from methane was experimentally achieved in a bubble column filled with molten potassium chloride. The melt acted as a carbon-separating agent and as a pyrolytic catalyst, and enabled 40 h of continuous running without catalytic deactivation with an apparent activation energy of 277 kJ/mole. The resultant solid was purified by water washing or acid washing, or heating at high temperature to remove salt residues from the carbon. Heating the solid product at 1200 °C produced the highest purity carbon (97.2 at%). The economic feasibility of methane pyrolysis was evaluated by varying key parameters, that is, melt loss, melt price, and carbon revenue. Given a potassium chloride loss of 0.45 per kg of produced carbon. In this case, methane pyrolysis using molten potassium chloride may be comparable to steam methane reforming with carbon capture storage.

Polyimide membranes have been widely investigated in gas separation applications due to their high separation abilities, excellent processability, relatively low cost, and stabilities. Unfortunately, it is extremely challenging to simultaneously achieve both improved gas permeability and selectivity due to the trade-off relationship in common polymer membranes. Diamine modification is a simple strategy to tune the separation performance of polyimide membranes, but an excessive loss in permeability is also generally observed. In the present work, we reported the effects of diamine type (i.e., non-fluorinated and fluorinated) on the physicochemical properties and the corresponding separation performance of a modified membrane using a commercial Matrimid^® 5218 polyimide. Detailed spectroscopic, thermal, and surface analyses reveal that the bulky fluorine groups are responsible for the balanced chain packing modes in the resulting Matrimid membranes compared to the non-fluorinated diamines. Consequently, the modified Matrimid membranes using fluorinated diamines exhibit both higher gas permeability and selectivity than those of pristine Matrimid, making them especially effective for improving the separation performance towards H₂/CH₄ and CO₂/CH₄ pairs. The results indicate that the use of fluorinated modifiers may offer new opportunities to tune the gas transport properties of polyimide membranes.