Martinez-Diaz David, Michienzi Valeria, Calles José Antonio, Sanz Raúl, Caravella Alessio, Alique David
Department of Applied Mathematics, Science and Engineering of Materials and Electronic Technology, Rey Juan Carlos University, 28933 Móstoles, Spain.
Department of Computer Engineering, Modelling, Electronics, and Systems Engineering (DIMES), University of Calabria, 87036 Rende, Italy.
Membranes (Basel). 2022 May 18;12(5):530. doi: 10.3390/membranes12050530.
Pd-membranes are interesting in multiple ultra-pure hydrogen production processes, although they can suffer inhibition by certain species or abrasion under fluidization conditions in membrane reactors, thus requiring additional protective layers to ensure long and stable operation. The ability to incorporate intermediate and palladium films with enough adherence on both external and internal surfaces of tubular porous supports becomes crucial to minimize their complexity and cost. This study addresses the incorporation of CeO and Pd films onto the internal side of PSS tubes for applications in which further protection could be required. The membranes so prepared, with a Pd-thickness around 12-15 μm, show an excellent mechanical resistance and similar performance to those prepared on the external surface. A good fit to Sieverts' law with an H-permeance of 4.571 × 10 mol m s Pa at 400 °C, activation energy around 15.031 kJ mol, and complete ideal perm-selectivity was observed. The permeate fluxes reached in H mixtures with N, He, or CO decreased with dilution and temperature due to the inherent concentration-polarization. The presence of CO in mixtures provoked a higher decrease because of a further inhibition effect. However, the original flux was completely recovered after feeding again with pure hydrogen, maintaining stable operation for at least 1000 h.
钯膜在多种超纯氢生产工艺中备受关注,尽管在膜反应器的流化条件下,它们可能会受到某些物质的抑制或磨损,因此需要额外的保护层以确保长期稳定运行。在管状多孔载体的内外表面上结合具有足够附着力的中间层和钯膜的能力,对于降低其复杂性和成本至关重要。本研究探讨了将CeO和钯膜结合到PSS管内侧,用于可能需要进一步保护的应用。如此制备的膜,钯层厚度约为12 - 15μm,表现出优异的机械抗性,并且与在外部表面制备的膜具有相似的性能。在400°C下,H渗透率为4.571×10 mol m s Pa,活化能约为15.031 kJ mol,完全符合Sieverts定律,且具有理想的渗透选择性。在与N、He或CO的H混合物中达到的渗透通量,由于固有的浓差极化,随着稀释和温度的降低而降低。混合物中CO的存在由于进一步的抑制作用导致下降幅度更大。然而,再次通入纯氢后,原始通量完全恢复,保持稳定运行至少1000小时。