The concept of liquid metal membranes for hydrogen separation, based on gallium or indium, was recently introduced as an alternative to conventional palladium-based membranes. The potential of this class of gas separation materials was mainly attributed to the promise of higher hydrogen diffusivity. The postulated improvements are only beneficial to the flux if diffusion through the membrane is the rate-determining step in the permeation sequence. Whilst this is a valid assumption for hydrogen transport through palladium-based membranes, the relatively low adsorption energy of hydrogen on both liquid metals suggests that other phenomena may be relevant. In the current study, a microkinetic modeling approach is used to enable simulations based on a five-step permeation mechanism. The calculation results show that for the liquid metal membranes, the flux is limited by the dissociative adsorption over a large temperature range, and that the membrane flux is expected to be orders of magnitude lower compared to the membrane flux through pure palladium membranes. Even when accounting for the lower cost of the liquid metals compared to palladium, the latter still outperforms both gallium and indium in all realistic scenarios, in part due to the practical difficulties associated with making liquid metal thin films.

Nowadays, nearly 50% of the hydrogen produced worldwide comes from Steam Methane Reforming (SMR) at an environmental burden of 10.5 t_CO2,eq/t_H2, accelerating the consequences of global warming. One way to produce clean hydrogen is via methane pyrolysis using melts of metals and salts. Compared to SMR, significant less CO₂ is produced due to conversion of methane into hydrogen and carbon, making this route more sustainable to generate hydrogen. Hydrogen is produced with high purity, and solid carbon is segregated and deposited on the molten bath. Carbon may be sold as valuable co-product, making industrial scale promising. In this work, methane pyrolysis was performed in a quartz bubble column using molten gallium as heat transfer agent and catalyst. A maximum conversion of 91% was achieved at 1119 °C and ambient pressure, with a residence time of the bubbles in the liquid of 0.5 s. Based on in-depth analysis of the carbon, it can be characterized as carbon black. Techno-economic and sensitivity analyses of the industrial concept were done for different scenarios. The results showed that, if co-product carbon is saleable and a CO₂ tax of 50 euro per tonne is imposed to the processes, the molten metal technology can be competitive with SMR.