Abstract: Boron-based metal-free catalysts for oxidative dehydrogenation of propane (ODHP) have drawn great attention in both academia and industry due to their impressive activity and olefin selectivity. Herein, the SiO₂ and B₂O₃ sequentially coated honeycomb cordierite catalyst is designed by a two-step wash-coat method with different B₂O₃ loadings (0.1%-10%) and calcination temperatures (600, 700, 800 ℃). SiO₂ obtained by TEOS hydrolysis acts as a media layer to bridge the cordierite substrate and boron oxide via abundant Si-OH groups. The welldeveloped straight channels of honeycomb cordierite make it possible to carry out the reactor under high gas hourly space velocity (GHSV) and the thin wash-coated B₂O₃ layer can effectively facilitate the pore diffusion on the catalyst. The prepared B₂O₃/SiO₂@HC monolithic catalyst exhibits good catalytic performance at low boron oxide loading and achieves excellent propylene selectivity (86.0%), olefin selectivity (97.6%, propylene and ethylene) and negligible CO₂ (0.1%) at 16.9% propane conversion under high GHSV of 345,600 ml·(g B₂O₃)^-1·h^-1, leading to a high propylene space time yield of 15.7 g C₃H₆·(g B₂O₃)^-1·h^-1 by suppressing the overoxidation. The obtained results strongly indicate that the boron-based monolithic catalyst can be properly fabricated to warrant the high activity and high throughput with its high gas/surface ratio and straight channels.

Key words: Oxidative dehydrogenation, Boron-based catalyst, Alkane, Propylene, Monolith, High GHSV

摘要： Boron-based metal-free catalysts for oxidative dehydrogenation of propane (ODHP) have drawn great attention in both academia and industry due to their impressive activity and olefin selectivity. Herein, the SiO₂ and B₂O₃ sequentially coated honeycomb cordierite catalyst is designed by a two-step wash-coat method with different B₂O₃ loadings (0.1%-10%) and calcination temperatures (600, 700, 800 ℃). SiO₂ obtained by TEOS hydrolysis acts as a media layer to bridge the cordierite substrate and boron oxide via abundant Si-OH groups. The welldeveloped straight channels of honeycomb cordierite make it possible to carry out the reactor under high gas hourly space velocity (GHSV) and the thin wash-coated B₂O₃ layer can effectively facilitate the pore diffusion on the catalyst. The prepared B₂O₃/SiO₂@HC monolithic catalyst exhibits good catalytic performance at low boron oxide loading and achieves excellent propylene selectivity (86.0%), olefin selectivity (97.6%, propylene and ethylene) and negligible CO₂ (0.1%) at 16.9% propane conversion under high GHSV of 345,600 ml·(g B₂O₃)^-1·h^-1, leading to a high propylene space time yield of 15.7 g C₃H₆·(g B₂O₃)^-1·h^-1 by suppressing the overoxidation. The obtained results strongly indicate that the boron-based monolithic catalyst can be properly fabricated to warrant the high activity and high throughput with its high gas/surface ratio and straight channels.

关键词: Oxidative dehydrogenation, Boron-based catalyst, Alkane, Propylene, Monolith, High GHSV