3D printed cross-scale structured TS-1 catalysts for continuous scale-up reactions

Structured catalysts and reactors have great application prospects in gas-liquid conversion engineering due to excellent process intensification. However, the conventional fabrication process limits the designability of the hierarchical structure of monolithic catalysts, the establishment of structure-activity relationships, and slows down the speed of catalyst development. Here, we establish a structure-activity mechanism for cross-scale structures of a 3D-printed functionally gradient modular monolithic TS-1 catalyst (FGMMC) and catalytic performance by adjusting hierarchical structure distribution based on catalytic reaction simulations. The effects of uniform and gradient structures with different TS-1 contents and unit cell sizes on the catalytic properties of modular monolithic TS-1 catalyst (MMC) were investigated. In one-step scale-up reactions of ethylene to highvalue-added ethylene glycol (EG), FGMMC exhibits superior catalytic efficiency than traditional powder, extrusion-dripping beads, and uniform catalysts. After a 27-h continuous scale-up catalytic test, FGMMCs exhibit excellent wear resistance (only 1.39% mass loss) and an outstanding EG yield of 82.5%. 3D-printed FGMMCs act as self-activators with a 37% reaction rate increase after rapid post-activation treatments. This work provides a low-cost and recyclable manufacturing method for achieving the functional and structural integration of catalysts and reactors by 3D printing while predicting and rapidly validating scale-up reactions.