咪唑类离子液体催化四氢噻吩氧化脱硫模拟
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中国石油大学华东新能源学院

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TE53

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本研究由国家科技部国家科技重大项目(2016ZX05012-002)、国家自然科学基金(51874333)、山东省自然科学基金(No.51874333)资助。ZR2017MEE030)


Mechanism of Oxidative Desulfurization of Tetrahydrothiophene catalyzed by imidazole ionic liquid
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College of New Energy in China University of Petroleum Engineering

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    摘要:

    离子液体作为催化剂在石油脱硫过程中有独特优势,特别是对噻吩类硫化物。本文以四氢噻吩为模型化合物,过氧化氢为氧化物,利用密度泛函理论,研究了咪唑氯铝酸盐离子液体催化四氢噻吩氧化成砜的反应机理,探讨不同阳离子的离子液体对催化效果的影响。构造离子液体在催化过程中与反应物、产物的络合结构,发现离子液体对产物砜具有更强的相互作用,阳离子侧链越长络合结构越稳定;对络合物的电荷布局、前线轨道性质的计算,发现络合后THT上S原子有电荷富集,电子整体上从THT转移到离子液体;并在分子层面解释离子液体对反应物键能、键长、电荷布局的作用机理;最后计算反应能垒,证明了加入离子液体可使得反应能垒降低31%以上,且阳离子侧链越长,效果越显著。

    Abstract:

    Ionic liquids have unique advantages as catalysts in petroleum desulfurization, especially for thiophene sulfides. In this paper, tetrahydrothiophene (THT) was selected as a model compound and hydrogen peroxide as the oxide. Using density functional theory, Ionic liquid was selected as catalyst, and the catalytic mechanism in the oxidation of tetrahydrothiophene to sulfone was studied. Cationic chain length was changed, and the influence of different side chains on catalytic effect was explored. The selective complexation mode of ionic liquids with reactants and products showed that ionic liquids have stronger extraction with the oxidation product sulfone. The longer the cationic side chain, the more stable the complex structure. The charge population and the properties of Frontier Molecular Orbital of the complex showed S on THT had charge enrichment, but the electrons transferred from THT to the ionic liquid during the complexation process. Then we explored the influence of ionic liquid on the bond energy, and charge population of the reactants, at a molecular level; Finally, the energy barrier of the reaction process proved ionic liquid reduced the reaction energy barrier by more than 31%, and the longer cationic side chain, the more significant the effect.

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  • 收稿日期:2020-09-13
  • 最后修改日期:2020-11-17
  • 录用日期:2020-12-23
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