Abstract: The present work is focused on the investigation of the performance and long-term stability of two composite palladium membranes under different operating conditions. One membrane (Pd/porous stainless steel (PSS)) is characterized by a ~10 µm-thick palladium layer on a porous stainless steel substrate, which is pretreated by means of surface modification and oxidation; the other membrane (Pd/Al2O3) is constituted by a ~7 µm-thick palladium layer on an asymmetric microporous Al2O3 substrate. The operating temperature and pressure ranges, used for studying the performance of these two kinds of membranes, are 350–450 °C and 200–800 kPa, respectively. The H2 permeances and the H2/N2 selectivities of both membranes were investigated and compared with literature data. At 400 °C and 200 kPa as pressure difference, Pd/PSS and Pd/Al2O3 membranes exhibited an H2/N2 ideal selectivity equal to 11700 and 6200, respectively, showing stability for 600 h. Thereafter, H2/N2 selectivity of both membranes progressively decreased and after around 2000 h, dropped dramatically to 55 and 310 for the Pd/PSS and Pd/Al2O3 membranes, respectively. As evidenced by Scanning Electron Microscope (SEM) analyses, the pinholes appear on the whole surface of the Pd/PSS membrane and this is probably due to release of sulphur from the graphite seal rings.
Abstract: In the research of new nanocomposite proton-conducting membranes, SnO2 ceramic powders with surface functionalization have been synthesized and adopted as additives in Nafion-based polymer systems. Different synthetic routes have been explored to obtain suitable, nanometer-sized sulphated tin oxide particles. Structural and morphological characteristics, as well as surface and bulk properties of the obtained oxide powders, have been determined by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) and Raman spectroscopies, N2 adsorption, and thermal gravimetric analysis (TGA). In addition, dynamic mechanical analysis (DMA), atomic force microscopy (AFM), thermal investigations, water uptake (WU) measurements, and ionic exchange capacity (IEC) tests have been used as characterization tools for the nanocomposite membranes. The nature of the tin oxide precursor, as well as the synthesis procedure, were found to play an important role in determining the morphology and the particle size distribution of the ceramic powder, this affecting the effective functionalization of the oxides. The incorporation of such particles, having sulphate groups on their surface, altered some peculiar properties of the resulting composite membrane, such as water content, thermo-mechanical, and morphological characteristics.
Abstract: The solidification behavior of poly(vinylidene fluoride) (PVDF) solution during membrane preparation by thermally induced phase separation (TIPS) was investigated. Apparatus newly developed in our laboratory was used to quantitatively measure membrane stiffness during phase separation. In this apparatus, a cooling polymer solution, placed on a stage, is moved upwards and the surface of the polymer solution contacts a sphere attached to the tip of a needle. The displacement of a blade spring attached to the needle is then measured by a laser displacement sensor. Different phase separation modes, such as liquid-liquid (L-L) phase separation and solid-liquid (S-L) phase separation (polymer crystallization) were investigated. In the case of S-L phase separation, the stiffness of the solution surface began to increase significantly just before termination of crystallization. In contrast, L-L phase separation delayed solidification of the solution. This was because mutual contact of the spherulites was obstructed by droplets of polymer-lean phase formed during L-L phase separation. Thus, the solidification rate was slower for the L-L phase separation system than for the S-L phase separation system.
Abstract: In membrane reactors, the interaction of reaction and membrane separation can be exploited to achieve a “process intensification”, a key objective of sustainable development. In the present work, the properties that the membrane must have to obtain this result in a pervaporation reactor are analyzed and discussed. Then, the methods to enhance these properties are investigated for the photocatalytic synthesis of vanillin, which represents a case where the recovery from the reactor of vanillin by means of pervaporation while it is produced allows a substantial improvement of the yield, since its further oxidation is thus prevented. To this end, the phenomena that control the permeation of both vanillin and the reactant (ferulic acid) are analyzed, since they ultimately affect the performances of the membrane reactor. The results show that diffusion of the aromatic compounds takes place in the presence of low concentration gradients, so that the process is controlled by other phenomena, in particular by the equilibrium with the vapor at the membrane-permeate interface. On this basis, it is demonstrated that the performances are enhanced by increasing the membrane thickness and/or the temperature, whereas the pH begins to limit the process only at values higher than 6.5.
Abstract: In this study, the polyvinylidene fluoride (PVDF) hollow fiber hemodialysis membranes were prepared by non-solvent induced phase separation (NIPS). The influences of PVDF membrane thickness and polyethylene glycol (PEG) content on membrane morphologies, pore size, mechanical and permeable performance were investigated. It was found that membrane thickness and PEG content affected both the structure and performance of hollow fiber membranes. The tensile strength and rejection of bovine serum albumin (BSA) increased with increasing membrane thickness, while the Ultrafiltration flux (UF) flux of pure water was the opposite. The tensile strength, porosity and rejection of BSA increased with increasing PEG content within a certain range. Compared with commercial F60S membrane, the PVDF hollow fiber membrane showed higher mechanical and permeable performance. It was proven that PVDF material had better hydrophilicity and lower BSA adsorption, which was more suitable for hemodialysis. All the results indicate that PVDF hollow fiber membrane is promising as a hemodialysis membrane.