Ceramic membranes have been considered as potential candidates for several gas separation processes of industrial interest, due to their increased thermal and chemical stability compared to polymeric ones. In the present study, commercial Hybrid Silica (HybSi^®) membranes have been evaluated and modified accordingly, to enhance their gas separation performance for targeted applications, including CO₂ removal from flue gas and H₂ recovery from hydrogen-containing natural gas streams. The developed membranes have been characterized before and after modification by relative permeability, single gas permeation, and equimolar separation tests of the respective gas mixtures. The modification procedures, involving in situ chemical vapor deposition and superficial functionalization, aim for precise control of the membranes’ pore size and surface chemistry. High performance membranes have been successfully developed, presenting an increase in H₂/CH₄ permselectivity from 12.8 to 45.6 at 250 °C. Ultimately, the modified HybSi^® membrane exhibits a promising separation performance at 250 °C, and 5 bar feed pressure, obtaining above 92% H₂ purity in the product stream combined with a notable H₂ recovery of 65%, which can be further improved if a vacuum is applied on the permeate side, leading to 94.3% H₂ purity and 69% H₂ recovery.

The shipping sector is responsible for a considerable share of global CO₂ emissions and is under pressure to reduce emissions and adopt carbon-neutral fuels. Among the proposed alternatives, methanol produced from green hydrogen and biogenic CO₂ represents a promising option. However, the feasibility of its production is significantly influenced by the composition and variability of the bio-CO₂ feedstock, which can negatively impact the complete value chain. To address these challenges, sampling campaigns were carried out at actual bio-CO₂-emitting sites, namely biogas and biomass combustion facilities, to characterize the impurity profiles and determine the appropriate conditioning requirements. A novel membrane gas absorption system with a Diethanolamine solution was deployed directly in the field to capture, as well as purify to a certain extent, the CO₂ stream. The system demonstrated high efficiency in removing most impurities, achieving high CO₂ capture rates and impurity reduction close to 90%. However, residual chlorine species were detected in the CO₂ streams from biogas plants, suggesting the need for additional conditioning to meet the purity specifications required for methanol synthesis. Given that the feedstock composition and upstream process conditions could significantly affect the final output and present considerable variations, the implementation of additional cleaning measures is recommended before synthesis.