查看更多>>摘要：Developing routes of utilizing CO2 emissions is important for long-term environmental preservation, as storing such emissions underground will eventually become unsustainable. One way of utilizing CO2 emissions is as a light-oxidant feedstock for oxidative dehydrogenation of propane (ODHP) to propylene. However, the adsorption and reaction steps typically occur at widely different temperatures, meaning that the thermal gradients - and by extension process energy requirements - are often unreasonably high. In recent years, dual-functional materials (DFMs) - i.e., materials comprised of a high temperature adsorbent phase alongside a heterogeneous catalyst - have been employed for combined CO2 adsorption and utilization over one material within a single bed using a reduced thermal gradient. However, these materials have never been formed into practical contactors and have never been applied to ODHP applications. Therefore, in this study we manufactured the first-generation of DFM adsorbent/catalyst monoliths, comprised of CaO (adsorbent) and M@ZSM-5 (M = V-, Ga-, Ti-, or Ni-oxide) heterogeneous catalysts, using our novel direct metal-oxide 3D printing technique. The monoliths were vigorously characterized using N-2 physisorption, C3H8-DRIFTS, NH3-TPD, Py-FTIR, H-2-TPR, XRD, XPS, and elemental mapping and were assessed for CO2 capture/ODHP utilization at 600-700 degrees C. The adsorption/catalysis experiments revealed that these materials can perform both processes effectively at 600 degrees C, with reduced propylene yield at higher temperature, which eliminated the need for a thermal gradient between the adsorption and catalysis steps. Between the various samples, the Ti-doped monolith generated the best balance of CO2 conversion (76%) and propylene selectivity (39%), due to the high dispersion of TiO2 , favorable redox properties and controlled acidity of the dopant. However, it was also found that varying the metal dopant could be used to control the heuristics of CO2/C3H8 conversion, C3H6 selectivity, and C3H6 yield, meaning that the manufacturing process outlined herein represents a promising way of tuning the chemical properties of structured DFM adsorbent/catalyst materials. More importantly, this study establishes a promising proof-of-concept for 3D printing as a facile means of structuring these exciting composite materials and expands DFMs to the previously unexplored application of ODHP.
NSTL
Elsevier