Abstract:
The CO
2-assisted oxidation dehydrogenation of ethane to ethylene can achieve the low-carbon production of ethylene industry by reducing emissions from the source and the end products while realizing the resource utilization of CO
2. Therefore, the research on the CO
2-assisted oxidation dehydrogenation of ethane to ethylene not only holds significant theoretical significance but also boasts broad industrial application prospects. High-silica ZSM-5 zeolite are regarded as ideal carriers for ethane oxidative dehydrogenation reaction due to their tunable acidity, excellent stability, and unique pore structure. However, its Si/Al ratio significantly affects the distribution of acidic sites on the catalyst and the dispersion of metal species. The alkali treatment method can selectively remove Si or Al from the zeolite framework, thereby modifying its acidity. The effects of alkali treatment conditions on the structure, acidity and catalytic performance of high-silica ZSM-5 were investigated by modulating the acidity and alkalinity of zeolite through modulating the temperature of alkali-treated ZSM-5 carriers (40, 60, 80 ℃) and introducing zinc active sites on alkali-treated ZSM-5. The physical properties of the catalysts were characterized using methods including X-ray diffraction, N
2 physisorption, field-emission scanning electron microscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma optical emission spectrometry, NH
3-temperature programmed desorption, ultraviolet-visible absorption spectroscopy, and X-ray photoelectron spectroscopy. Additionally, the catalytic performance of the catalysts for the oxidative dehydrogenation of ethane to ethylene were evaluated in a fixed-bed reactor. Finally, the structure-activity relationship of the ZnZ5-270-
T catalyst was established. The results show that the alkali treatment preferentially removed the silicon species in the ZSM-5 skeleton and successfully introduced mesopores in ZSM-5 to form a multistage pore structure. This structure led to an increase in the zinc loading of the alkali-treated ZnZ5-270-
T catalyst. Meanwhile, alkali treatment could change the type of ZnZ5-270-
T zinc species from ZnO to ZnOH
+ with higher catalytic activity. The reaction network of the ZnZ5-270-
T catalysts was revealed by analyzing the H
2/C
2H
4 and CO/C
2H
4 mole ratios of the reaction products, indicating that indirect oxidative dehydrogenation was the main reaction pathway for all catalysts. It was also found that the loss of Zn species could be the main reason for catalyst deactivation.