Kinetic model for Pd-based membranes coking/deactivation in propane dehydrogenation processes

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.