(452a) 3D-Printed Zeolite Monoliths with Metal Dopants for Methanol Conversion

Additive manufacturing by 3D printing has gained worldwide attention in formulation of porous materials into practical contactors as a result of flexibility in design alteration and preparation of robust and complex geometries which requires fewer steps and minimal resources in comparison to the previously established extrusion process.[1-4] In this study, 3D-printed ZSM-5 monoliths doped with Ga₂O₃, Cr₂O₃, CuO, ZnO, MoO₃, and Y₂O₃ were synthesized using the state-of-art 3D printing technique. The physicochemical properties of the catalysts were characterized by X-ray diffraction, N₂ physisorption, NH₃ and CO₂ temperature-programed desorption and H₂ temperature-programmed reduction. The promotional effect of doped metals on catalytic performance of 3D-printed ZSM-5 monoliths in methanol to hydrocarbon (MTH) reaction in the presence and absence of CO₂ was investigated. Results indicated that both metal dopants type and reaction atmosphere greatly influence catalyst stability and product distribution. The yield of light olefins was enhanced over all metal-doped 3D-printed ZSM-5 monoliths in N₂ atmosphere (absence of CO₂), however, CO₂ atmosphere did not favor the production of light olefins. Although selectivity toward ethylene slightly decreased, the propylene yield was almost constant after switching N₂ to CO₂ in MTH reaction at 400 °C. Furthermore, it was found that Y- and Zn-doped ZSM-5 monoliths exhibited higher yield of light olefins and BTX compounds in the in the absence and presence of CO₂, respectively.

References:

[1] F. Magzoub, X. Li, J. Al-Darwish, F. Rezaei, A.A. Rownaghi, 3D-printed ZSM-5 monoliths with metal dopants for methanol conversion in the presence and absence of carbon dioxide, Appl. Catal. B Environ. 245 (2019) 486–495.

[2] X. Li, A. Alwakwak, F. Rezaei, A.A. Rownaghi, Synthesis of Cr , Cu , Ni , and Y ‑ Doped 3D-Printed ZSM-5 Monoliths and Their Catalytic Performance for n-Hexane Cracking, ACS Appl. Energy Mater. 1 (2018) 2740–2748.

[3] X. Li, F. Rezaei, A.A. Rownaghi, 3D-printed zeolite monoliths with hierarchical porosity for selective methanol to light olefin reaction, React. Chem. Eng. 3 (2018) 733–746.

[4] X. Li, F. Rezaei, A. Rownaghi, Methanol-to-olefin conversion on 3D-printed ZSM-5 monolith catalysts: Effects of metal doping, mesoporosity and acid strength, Microporous Mesoporous Mater. 276 (2019) 1–12.