Novel reactor configurations for the oxidative coupling of methane (OCM), and in particular membrane reactors, contribute toward reaching the yield required to make the process competitive at the industrial scale. Therefore, in this work, the conventional OCM packed bed reactor using a Mn-Na₂WO₄/SiO₂ catalyst was experimentally compared with a membrane reactor, in which a symmetric MgO porous membrane was integrated. The beneficial effects of distributive feeding of oxygen along the membrane, which is the main advantage of the porous membrane reactor, were demonstrated, although no significant differences in terms of performance were observed because of the adverse effects of back-permeation prevailing in the experiments. A sensitivity analysis carried out on the effective diffusion coefficient also indicated the necessity of properly tuning the membrane properties to achieve the expected promising results, highlighting how this tuning could be addressed.

H₂ production via membrane-assisted steam methane reforming (MA-SMR) can ensure higher energy efficiency and lower emissions compared to conventional reforming processes (SMR). Ceramic-supported Pd–Ag membranes have been extensively investigated for membrane-assisted steam methane reforming applications, with outstanding performance. However, costs, sealings for integration in the reactor structure, and resistance to solicitations remain challenging issues. In this work, the surface quality of a low-cost, porous Hastelloy-X filter is improved by asymmetric filling with α-Al₂O₃ of decreasing size and deposition of γ-Al₂O₃ as an interdiffusion barrier. On the modified support, a thin Pd–Ag layer was deposited via electroless plating (ELP), resulting in a membrane with H₂/N₂ selectivity >10,000. The permeation characteristics of the membrane were studied, followed by testing for membrane-assisted methane steam reforming. The results showed the ability of the membrane reactor to overcome thermodynamic conversion of the conventional process for all explored operating conditions, as well as ensuring 99.3% H₂ purity in the permeate stream at 500 °C and 4 bar.

The rates of CO₂ mass deposition onto cryogenically cooled surfaces are crucial for CO₂ removal processes that rely on cryogenics. A dedicated experimental setup was constructed to measure CO₂ mass deposition rates under controlled conditions. Experiments were carried out with both pure CO₂ and CO₂/N₂ mixtures, growing frost layers up to 8 mm thick. Results demonstrated that heat transfer through the frost layer significantly slows down the mass deposition process. Furthermore, it was found that the addition of N₂ to the gas phase has a considerable influence on mass deposition rates, because it introduces an additional mass transfer resistance toward the frost surface. To describe the experimentally observed behavior, a frost growth model based on mass and energy balances was developed. Expressions for the frost density as a function of the frost temperature and for the effective frost conductivity as a function of the frost density were derived and implemented in the model. When accounting for drift fluxes, the model accurately captures the behavior observed in experiments. The findings of this work highlight the significant impact of heat transfer limitations on processes that accumulate a thick solid CO₂ layer, such as continuously cooled heat exchangers. Conversely, technologies like cryogenically refrigerated packed beds do not develop a thick solid CO₂ layer; calculations showed that a frost layer of 3.24·10⁻⁵ m is formed, resulting in a Biot number well below 0.01, indicating that heat transfer in the frost layer is not limiting.