Luigi Marsico, Adele Brunetti, Enrico Catizzone, Massimo Migliori, Giuseppe Barbieri
This work presents the design of a membrane-integrated process for biogas valorisation and renewable hydrogen storage via CO 2 -to-methanol conversion. The process maximizes CO 2 utilisation by incorporating H 2 from renewable sources, while simultaneously separating methane from biogas to produce a stream suitable for direct injection into the natural gas grid. Membrane units are integrated upstream and downstream of the methanol synthesis reactor: upstream membranes allow to obtain a CO 2 -rich stream for methanol production and a CH 4 -rich stream compliant with grid specifications, while downstream membranes recover unreacted CO 2 and H 2 for recycling, minimizing emissions and hydrogen losses. The system is analysed in a step/stage configuration using performance maps from a validated one-dimensional model, accounting for the selectivity and permeance of a polyimide membrane. Results show that biogas can be fully valorised, achieving 98.5% CH 4 recovery with molar purity ≥97.5% and ∼97% CO 2 conversion to methanol, with nearly complete utilisation of renewable hydrogen. This membrane-integrated approach provides an effective strategy for coupling biogas upgrading with renewable hydrogen storage, enabling sustainable energy storage in the form of methanol e-fuels and contributing to carbon-neutral energy pathways.