This work presents multi-scale approaches to investigate 3D printed structured Mn–Na–W/SiO₂ catalysts used for the oxidative coupling of methane (OCM) reaction. The performance of the 3D printed catalysts has been compared to their conventional analogues, packed beds of pellets and powder. The physicochemical properties of the 3D printed catalysts were investigated using scanning electron microscopy, nitrogen adsorption and X-ray diffraction (XRD). Performance and durability tests of the 3D printed catalysts were conducted in the laboratory and in a miniplant under real reaction conditions. In addition, synchrotron-based X-ray diffraction computed tomography technique (XRD-CT) was employed to obtain cross sectional maps at three different positions selected within the 3D printed catalyst body during the OCM reaction. The maps revealed the evolution of catalyst active phases and silica support on spatial and temporal scales within the interiors of the 3D printed catalyst under operating conditions. These results were accompanied with SEM-EDS analysis that indicated a homogeneous distribution of the active catalyst particles across the silica support.

In this study, three different reactor concepts for the oxidative coupling of methane (OCM) reaction are examined at the miniplant scale. Their performance and response to variations in key process parameters, such as temperature and gas hourly space velocity (GHSV), are evaluated over a wide range. In addition to the conventional Packed Bed Reactor (PBR), Packed Bed Membrane Reactor (PBMR), and Chemical Looping Reactor (CLR) approaches were tested. The PBMR was realized with a porous ceramic $\alpha$-Alumina membrane as air/O₂ distributor. The CLR was operated in a poly-cyclic operation. Similarities of the different reactor concepts as well as layout-immanent differences with regard to changes in reaction conditions could be identified and advantages and disadvantages of the processes highlighted. The results show that C₂ selectivity can be improved by both PBMR and CLR in comparison to conventional PBR, possibly reducing cost-intensive downstream units. While a PBMR can slightly improve selectivity (23%) while keeping the same conversion compared to a PBR, the use of a CLR allows for achieving exceptionally high selectivities of up to 90%. In order to address the low conversion, CLR tests were carried out with an additional O₂ carrier material, which led to a significant improvement in terms of C₂ yield. In addition to an evaluation and comparison of the different reactor concepts, the findings at the miniplant scale provide estimates of their potential use and scalability.