Lanthanum tungstate membranes for H2 extraction and CO2 utilization: Fabrication strategies based on sequential tape casting and plasma-spray physical vapor deposition

In the context of energy conversion efficiency and decreasing greenhouse gas emissions from power generation and energy-intensive industries, membrane technologies for H2 extraction and CO2 capture and utilization become pronouncedly important. Mixed protonic-electronic conducting ceramic membranes are hence attractive for the pre-combustion integrated gasification combined cycle, specifically in the water gas shift and H2 separation process, and also for designing catalytic membrane reactors. This work presents the fabrication, microstructure and functional properties of Lanthanum tungstates (La28−xW4+xO54+δ, LaWO) asymmetric membranes supported on porous ceramic and porous metallic substrates fabricated by means of the sequential tape casting route and plasma spray-physical vapor deposition (PS-PVD). Pure LaWO and W site substituted LaWO were employed as membrane materials due to the promising combination of properties: appreciable mixed protonic-electronic conductivity at intermediate temperatures and reducing atmospheres, good sinterability and noticeable chemical stability under harsh operating conditions. As substrate materials porous LaWO (non-substituted), MgO and Crofer22APU stainless steel were used to support various LaWO membrane layers. The effect of fabrication parameters and material combinations on the assemblies’ microstructure, LaWO phase formation and gas tightness of the functional layers was explored along with the related fabrication challenges for shaping LaWO layers with sufficient quality for further practical application. The two different fabrication strategies used in the present work allow for preparing all-ceramic and ceramic-metallic assemblies with LaWO membrane layers with thicknesses between 25 and 60 μm and H2 flux of ca. 0.4 ml/min cm2 measured at 825 °C in 50 vol% H2 in He dry feed and humid Ar sweep configuration. Such a performance is an exceptional achievement for the LaWO based H2 separation membranes and it is well comparable with the H2 flux reported for other newly developed dual phase cer-cer and cer-met membranes