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    碱处理高硅ZnZSM-5用于乙烷氧化脱氢反应

    Alkali-treated high-silica ZnZSM-5 for oxidative dehydrogenation of ethane

    • 摘要: CO2 氧化乙烷脱氢制乙烯在实现 CO2 资源化利用的同时可从源头减排和末端利用2方面实现乙烯工业的低碳化生产。因此研究CO2 氧化乙烷脱氢制乙烯不仅具有重要的理论意义,而且具有广阔的工业应用前景。高硅ZSM-5分子筛凭借其可调控的酸性、卓越的稳定性以及独特的孔道结构,被视为乙烷氧化脱氢反应的理想载体,但是其Si与Al物质的量比显著影响催化剂酸性位点分布及金属物种分散性。碱处理方法可选择性除去分子筛骨架中的Si或Al,从而改变其酸性。通过调控碱处理ZSM-5载体温度(40、60、80 ℃)调变沸石分子筛的酸碱性,并在碱处理后的ZSM-5上引入锌活性位点,采用X射线衍射、氮气物理吸脱附试验、场发射扫描电子显微镜、高角环形暗场扫描透射电子显微镜、能量色散X射线光谱、电感耦合等离子体发射光谱、NH3-程序升温脱附、紫外−可见吸收光谱和X射线光电子能谱等方法对催化剂进行了物性表征,并用固定床反应器评价催化剂对乙烷氧化脱氢制乙烯的催化性能,最终建立了ZnZ5-270-T催化剂的构效关系。结果表明:碱处理优先脱除ZSM-5骨架中的硅物种,成功在ZSM-5中引入介孔,形成多级孔结构。这种结构使得碱处理后的ZnZ5-270-T催化剂的锌负载量增加。同时碱处理可改变ZnZ5-270-T锌物种类型,使锌物种由ZnO转变为具有更高催化活性的ZnOH+。通过分析反应产物的H2/C2H4和CO/C2H4物质的量比,揭示了ZnZ5-270-T催化剂的反应网络,表明所有催化剂均以间接氧化脱氢为主要反应路径。研究还发现锌物种的流失可能是催化剂失活的主要原因。

       

      Abstract: The CO2-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 CO2. Therefore, the research on the CO2-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, N2 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, NH3-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 H2/C2H4 and CO/C2H4 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.

       

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