Structured ZSM-5/SiC foam catalysts for bio-oils upgrading

ZSM-5 zeolite coating supported on SiC foams was prepared by a precursor dispersion-secondary growth method and the resulting structured ZSM-5/SiC foam catalyst was used for the proof-of-concept study of catalytic bio-oils upgrading (i.e. deoxygenation of the model compounds of methanol and anisole) in reference to ZSM-5 catalyst pellets. A layer of ZSM-5 coating with inter-crystal porosity on SiC foams was produced by curing the zeolite precursor thermally at 80 °C. The use of SiC foam as the zeolite support significantly improved transport phenomena compared to the packed-bed using ZSM-5 pellets, explaining the comparatively good catalytic performance achieved by the structured ZSM-5/SiC foam catalyst. In comparison with the ZSM-5 pellets, the ZSM-5/SiC foam catalyst showed 100.0% methanol conversion (at the weight hourly space velocity, WHSV, of 8 h–1) and 100.0% anisole conversion (at WHSV =5 h−1) at the initial stage of the processes, while only about 3% were obtained for the ZSM-5 pellets, under the same conditions. Based on the comparative analysis of the characterisation data on the fresh and spent catalysts, the deactivation mechanisms of the ZSM-5/SiC and the ZSM-5 pellet catalysts were explained. The process intensification using SiC foam to support ZSM-5 improved the global gas-to-solid mass transfer notably, and hence mitigating the pore blocking due to the carbon deposition on the external surface of supported ZSM-5

Microtomography-based numerical simulations of heat transfer and fluid flow through β-SiC open-cell foams for catalysis

β-SiC open-cell foams are promising materials for catalytic supports with improved heat and mass transfer at moderate pressure drops. In this work, 3-dimensional (3D) models of a 30 ppi (pores per inch) β-SiC open-cell foam were generated using X-ray microtomography data. The resulting foam models were then used for finite element analysis (FEA) and computational fluid dynamics (CFD) simulations of heat transfer and fluid flow on the pore-scale. The FEA results demonstrate that (i) the overall effective thermal conductivity from direct simulations is comparable to the results estimated by experimental measurement, and are in the order of 10−1 W m−1 K−1 and (ii) thermal transport through fluid-saturated β-SiC foams depends on the solid-to-fluid conductivity ratio. By employing realistic foam models, pore-scale CFD simulations of fluid flows revealed the microscopic characteristics of laminar flow through open-cell foams. The anisotropic feature of realistic foam models promotes the axial and radial mixing of fluids in and after the foam element. The diffusion coefficient of laminar flow within foams was estimated at 10−4 m2 s−1, which is much larger than the molecular diffusion coefficient in a typical laminar flow in an open channel

Palladium-doped hierarchical ZSM-5 for catalytic selective oxidation of allylic and benzylic alcohols

From The Royal Society via Jisc Publications RouterHistory: received 2021-06-24, accepted 2021-08-17, collection 2021-10, pub-electronic 2021-10-20Article version: VoRPublication status: PublishedFunder: Engineering and Physical Sciences Research Council; Id: http://dx.doi.org/10.13039/501100000266; Grant(s): Nanoscience and Nanotechnology Facility, PR16195 - National Facility for XPS (“HarwellXPSFunder: Diamond Light Source; Id: http://dx.doi.org/10.13039/100011889; Grant(s): SP15151Hierarchical zeolites have the potential to provide a breakthrough in transport limitation, which hinders pristine microporous zeolites and thus may broaden their range of applications. We have explored the use of Pd-doped hierarchical ZSM-5 zeolites for aerobic selective oxidation (selox) of cinnamyl alcohol and benzyl alcohol to their corresponding aldehydes. Hierarchical ZSM-5 with differing acidity (H-form and Na-form) were employed and compared with two microporous ZSM-5 equivalents. Characterization of the four catalysts by X-ray diffraction, nitrogen porosimetry, NH3 temperature-programmed desorption, CO chemisorption, high-resolution scanning transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy allowed investigation of their porosity, acidity, as well as Pd active sites. The incorporation of complementary mesoporosity, within the hierarchical zeolites, enhances both active site dispersion and PdO active site generation. Likewise, alcohol conversion was also improved with the presence of secondary mesoporosity, while strong Brønsted acidity, present solely within the H-form systems, negatively impacted overall selectivity through undesirable self-etherification. Therefore, tuning support porosity and acidity alongside active site dispersion is paramount for optimal aldehyde production