Comprehensive permeation analysis and mechanical resistance of electroless pore-plated Pd-membranes with ordered mesoporous ceria as intermediate layer

Abstract H2-selective composite membranes, particularly those based on palladium films deposited onto porous stainless-steel supports, represent a promising technology to be practically included in both independent devices and membrane reactors. To reach thin H2-selective films and hence high permeance values, the use of a wide variety of intermediate layers is usually adopted in the literature. However, an agreement about the best solution is not found up to now. In this context, the current study presents the use of Ordered Mesoporous Ceria (OMC) particles as intermediate layer for the improvement of permeation properties of Electroless Pore-Plated (ELP-PP) Pd-composite membranes. OMC was obtained by nanocasting from SBA-15 as temporary template and cerium nitrate (III) hexahydrate as metal precursor. Resultant OMC particles have around 100 nm spherical diameter, an average pore-size diameter of 10-12 nm, and a total BET surface of around 134 m2/g. This material was next deposited onto the external surface of tubular Porous Stainless-Steel (PSS) supports by vacuum-assisted dip-coating (VA-DC) to form an intermediate layer that makes the preparation of a defect-free and thin Pd-film easier. This procedure allows the preparation of Pd composite membranes (OMC-Pd) with Pd thicknesses around 10 μm, H2 permeances of 1.03·10-3 mol m-2 s-1 Pa-0.5 at 400°C, and high ideal selectivity αH2/N2≥24,000. It should be noted that H2 permeance has been increased up to 6 times in comparison with other ELP-PP membranes without any intermediate layer and 2 times in contrast to membranes containing dense CeO2 particles instead of the mesoporous ones for the intermediate layer. Moreover, Pd-membranes so prepared (OMC-Pd) have shown excellent mechanical resistance in a wide variety of operating conditions such as temperature, pressure, and permeate flux direction, maintaining a high H2-selectivity without delamination or peeling. These properties were also maintained in case of feeding different H2/N2 mixtures, where the concentration-polarization effect seems to stabilize for lower H2 concentration values in the feed stream, not being noticeably influenced by temperature.