Screening of Adsorbent/Catalyst Composite Monoliths for Carbon Capture-Utilization and Ethylene Production

Combining CO₂ adsorption and utilization in oxidative dehydrogenation of ethane (ODHE) into a single bed is an exciting way of converting a harmful greenhouse gas into marketable commodity chemicals while reducing energy requirements from two-bed processes. However, novel materials should be developed for this purpose because most adsorbents are incapable of capturing CO₂ at the temperatures required for ODHE reactions. Some progress has been made in this area; however, previously reported dual-functional materials (DFMs) have always been powdered-state composites and no efforts have been made toward forming these materials into practical contactors. In this study, we report the first-generation of structured DFM adsorbent/catalyst monoliths for combined CO₂ capture and ODHE utilization. Specifically, we formulated M-CaO/ZSM-5 monoliths (M = In, Ce, Cr, or Mo oxides) by 3D-printing inks with CaCO₃ (CaO precursor), insoluble metal oxides, and ZSM-5. The physiochemical properties of the monoliths were vigorously characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N₂ physisorption, elemental mapping, pyridine Fourier transform infrared spectroscopy (Py-FTIR), H₂-temperature-programmed reduction (H₂-TPR), and NH₃-temperature-programmed desorption (NH₃-TPD). Their performances for combined CO₂ adsorption at 600 °C and ODHE reaction at 700 °C under 25 mL/min of 7% C₂H₆ were then investigated. The combined adsorption/catalysis experiments revealed the best performance in Cr-CaO/ZSM-5, which achieved 56% CO₂ conversion, 91.2% C₂H₄ selectivity, and 33.8% C₂H₄ yield. This exceptional performance, which was improved from powdered-state DFMs, was attributed to the high acidity and numerous oxidation states of the Cr₂O₃ dopant which were verified by NH₃-TPD and H₂-TPR. Overall, this study reports the first-ever proof-of-concept for 3D-printed DFM adsorbent/catalyst materials and furthers the area of CO₂ capture and ODHE utilization by providing a simple pathway to structure these composites.