MgX2O4 (X=Cr、Fe、Mn) 型尖晶石B位点阳离子对乙烷化学链氧化脱氢生成乙烯的影响

Impact of B-site cations of MgX2O4 (X=Cr, Fe, Mn) spinels on the chemical looping oxidative dehydrogenation of ethane to ethylene

  • 摘要: 化学链循环氧化脱氢技术(CL-ODH)是一个多功能的平台,它可以利用载氧体中晶格氧的选择性氧化这一特性,实现乙烷向乙烯的高值化转化。本研究探讨了MgX2O4(X=Cr、Fe或Mn)型尖晶石载氧体中B位元素对乙烷CL-ODH性能的影响。采用固定床和H2-TPR、O2-TPD、TG、原位拉曼、SEM、TEM等方法对MgX2O4尖晶石进行了性能测试和表征。结果表明,MgCr2O4仅释放微量表面吸附氧,更倾向于催化乙烷转化为焦炭和氢气。MgFe2O4通过提供更多的表面晶格氧,促进乙烷深度氧化成CO2。MgMn2O4载氧体在乙烷CL-ODH反应中能够释放出大量的体相晶格氧,它可以选择性燃烧氢气以推进反应正向进行,增加乙烯的选择性,实现了73.72%的乙烷转化率和81.46%的乙烯选择性。此外,MgMn2O4催化剂在乙烷CL-ODH反应中进行了30次的氧化还原循环实验,表现出稳定的反应性能,在整个循环测试中乙烯收率大约为62.00%。MgX2O4尖晶石氧化物中B位元素影响了其晶格氧的供应能力,从而影响了其在乙烷CL-ODH反应中的性能。

     

    Abstract: Chemical looping oxidative dehydrogenation (CL-ODH) provides a multifunctional conversion platform that can take advantage of the selective oxidation of lattice oxygen in oxygen carrier to achieve high-valued ethane to ethylene conversion. In this study, we explored the effect of B-site element in MgX2O4 (X=Cr, Fe, or Mn) spinel-type oxygen carriers on the performance of ethane CL-ODH. The properties test and characterization of MgX2O4 spinel were tested by fixed bed and H2-TPR, O2-TPD, TG, in-situ Raman, SEM, and TEM. The results showed that because MgCr2O4 only released a small amount of adsorbed surface oxygen, it tended to catalyze the conversion of ethane to coke and hydrogen. MgFe2O4 facilitated the deep oxidation of ethane into CO2 by providing more surface lattice oxygen. Meanwhile, since a significant amount of bulk lattice oxygen was released by the MgMn2O4 oxygen carrier, it could burn hydrogen in a targeted manner to advance the reaction and increased ethylene's selectivity. Thereby, MgMn2O4 achieved an ethane conversion of 73.72% with an ethylene selectivity of 81.46%. Furthermore, the MgMn2O4 catalyst demonstrated stable reactivity and an ethylene yield of about 62.00% in ethane CL-ODH over the 30 redox cycles. The screening tests indicated that the B-site elements in MgX2O4 spinel oxides could significantly influence their ability to supply lattice oxygen, thereby affecting their performance in ethane CL-ODH reaction.

     

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