The present work is a study of CO2 Reforming of Methane (DRM) carried out in a catalytic Pd-based membrane reactor. A detailed thermodynamic analysis is carried out, calculating the chemical equilibrium parameters in two different cases: (a) DRM along with the Reverse Water Gas Shift (RWGS) reaction and (b) DRM along with both RWGS and the Boudouard Reaction (BR). The performance of membrane reactor is then experimentally analyzed in terms of methane conversion, hydrogen recovery and H2/CO reaction selectivity by varying feed pressure and CO2/CH4 feed molar ratio and 500 °C and GHSV = 100 h−1. Among the obtained results, a CH4 conversion of about 26% and a H2 recovery of 47% are achieved at low feed pressures, exceeding the traditional reactor equilibrium conversion. This effect can be attributed to the favorable thermodynamics coupled to the hydrogen permeation through the membrane. This study further demonstrates the general effectiveness of membrane-integrated reaction processes, which makes the production of syngas more efficient and performing, providing important environmental benefits.

In this study, we propose to define a connectivity factor as the inverse of the diffusional tortuosity to measure quantitatively the connectivity of whatever type of structure. The concept of connectivity used here is related to the diffusional accessibility of the structure voids. This definition of connectivity factor arises from the consideration that, if we ideally imagine to decrease progressively the porosity of a regular structure, the porosity itself reaches a limit value below which the inner pores are not interconnected anymore. This leads to an evident situation of zero connectivity and infinite tortuosity, where there is no continuous diffusion path able to connect the structure voids. According to the proposed definition, the connectivity factor is comprised within [0, 1], with zero corresponding to a completely disconnected structure and unity to a completely connected one. To show the efficacy of the presented approach, a case study on the regular structure of mono-sized (mono-disperse) spherical particles (Simple Cubic (SC), Face-Centred Cubic (FCC), Body-Centred Cubic (BCC) and Tetragonal structures) is provided. In particular, the tortuosity of such structures is evaluated by Computational Fluid Dynamics simulations, calculating the connectivity factor consequently. The morphological modification with porosity is induced by changing the surface-surface interparticle distance, allowing us to take both positive (detached particles) and negative values (overlapping particles). For each structure, a comparison between the calculated trends and some correlations of literature is made, and a novel "hidden" morphological parameter has been identified, that is, the here-called Limit Porosity Value, below which the connectivity is zero. The presented approach represents a systematic methodology to quantify the connectivity of any structure and to compare the morphology of membranes, catalysts, and porous media in general.