open access

https://hdl.handle.net/2115/87958

High-loading Ga-exchanged MFI zeolites as selective and coke-resistant catalysts for nonoxidative ethane dehydrogenation

英語

2022-02-07

Royal Society of Chemistry

Catalysis science and technology

12(3)

986-995

In this paper, we investigated the effects of the Ga loading amount and H-2 treatment temperature for the reductive solid-state ion-exchange reaction on the generated Ga species in Ga-exchanged MFI zeolites (Ga-MFIs) as well as their catalysis for ethane dehydrogenation (EDH). For the formation of isolated Ga hydrides in the zeolites, [GaH](2+) ions were preferentially formed in the low-loading Ga-MFI (Ga/Al = 0.3) treated with H-2 at 550 degrees C, corresponding to the conventional preparation conditions, (Ga-MFI-0.3(550)), while the high Ga loading (Ga/Al = 1.0) and high-temperature H-2 treatment (800 degrees C) (Ga-MFI-1.0(800)) induced the formation of [GaH2](+) ions as the major Ga hydrides, as revealed by in situ Fourier transform infrared spectroscopy including the isotope experiment using D-2. In the context of other Ga species, such as Ga+ cations and partially reduced Ga oxides (GaOX), Ga+ cations and GaOX coexist in Ga-MFI-0.3(550), as indicated by pyridine adsorption experiments. On the other hand, GaOX was hardly observed and a larger amount of Ga+ cations was formed in Ga-MFI-1.0(800). The remaining Bronsted acid sites (BASs) were also characterized by the NH3 adsorption experiment. In the EDH reaction, Ga-MFI-1.0(800) exhibited high selectivity owing to low coke formation, resulting in the highest durability among the series of Ga-MFIs tested. Under the optimized conditions, Ga-MFI-1.0(800) exhibited the highest C2H4 formation rate among previously reported Pt-free catalysts. Based on the combined results of characterization, catalyst tests, and kinetic studies, the high selectivity and durability of Ga-MFI-1.0(800) can be ascribed to the low amount of the remaining BASs by isolated Ga species ([GaH](2+), [GaH2](+) ions and Ga+ cations) as well as the major formation of [GaH2](+) ions among isolated Ga hydrides.

学術雑誌論文

Accepted Manuscript

2044-4753