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This work aims at providing insight into the deactivation mechanism of Pd-based membranes in propane dehydrogenation processes. Thermogravimetric analysis (TGA) experiments were conducted to study the adsorption and coking of propylene over conventional thin layer (TL) and double-skinned (DS) Pd-based membranes under several operating conditions. A mechanistic monolayer-multilayer coke growth model was selected to mathematically describe the membrane coking observed during TGA experiments. In addition, the reaction rate of coke formation and its influence on membranes deactivation has been studied. The deactivation model able to describe the hydrogen flux decay over time suggests that monolayer coke is the main responsible for the membrane deactivation. Multilayer coke also causes deactivation but with a smaller order than monolayer coke, for both the TL and the DS membranes. Among the two membrane types, DS membrane deactivates faster, i.e. with a higher order than the TL membrane, which is equal to 1.55 for the former and 0.51 for the latter. This is related to the higher number of active sites available in the controlling step of the deactivation reaction, which are most probably given by the addition of the ceramic Al2O3 protective layer. XPS spectra further confirms that, in the presence of Pd, Al2O3 sites contribute to carbon formation by evidencing a different nature of carbon formed on the two membranes. Finally, the experimental results of hydrogen permeation over time conducted on different membranes types and operative conditions confirmed the validity of the derived and parametrized kinetic models for coke formation and membrane deactivation. The experimental findings and the kinetic model derived in this work provide essential tools for the design and optimization of membrane reactors for dehydrogenation processes.

This communication summarizes the use of double-skinned membranes for hydrogen separation in presence of TiO2 based catalyst (PtReCe/TiO2). The use of this type of membrane avoids the direct contact between catalyst particles and surface of the Pd-based hydrogen selective layer due to the presence of a mesoporous YSZ/γ-Al2O3 layer. The PdAg layer is protected by the mesoporous layer from direct contact with catalyst particles, avoiding erosion and possible chemical interactions. In comparison with a conventional PdAg membrane, the hydrogen flux of DS-membrane was observed not to be compromised during test carried out at 400 °C.

The coatings with gradually varying chemical composition and structure were obtained by PECVD method from methane precursor and various admixtures of Ar. The composition of emitted gases and triboemission behaviour were studied for these coatings and correlated with the coating properties and deposition conditions. A new analytical approach was developed that allowed identification of the emitted gas species with much higher accuracy than conventional techniques. For the first time, triboemission of alkanes higher than propane was observed. By the application of kinetic model to the analysis of triboemission time series, chemical and structural degradation in carbon coatings could be traced in course of tribological tests.

The permeation characteristics of palladium pore filled (PF) membranes have been investigated with gas permeation and structural characterization of the membranes. PF membranes have been prepared by filling with Pd the nanoporous γ-Al2O3/YSZ (or pure YSZ) layer supported onto porous α-Al2O3 and ZrO2. The number of nanoporous layers and the applied vacuum level during the electroless plating process have been studied. Gas permeation properties of the PF membranes have been determined in a temperature range of 300–550 °C. The measured hydrogen permeances have been found to be lower than previously reported for similar membranes. It has been found that the hydrogen fluxes do not depend on the thickness of the nanoporous layers (γ-Al2O3/YSZ or pure YSZ) or on the vacuum pump employed for filling with Pd. The physicochemical characterization performed showed that the palladium deposited does not form a percolated network across the mesoporous layer(s), leading to low hydrogen permeances and thus low H2/N2 perm-selectivities.