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氯氧化锆基三元低共熔溶剂的制备和氧化脱硫性能

王添渤 李秀萍 赵荣祥

王添渤, 李秀萍, 赵荣祥. 氯氧化锆基三元低共熔溶剂的制备和氧化脱硫性能[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2023085
引用本文: 王添渤, 李秀萍, 赵荣祥. 氯氧化锆基三元低共熔溶剂的制备和氧化脱硫性能[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2023085
WANG Tianbo, LI Xiuping, ZHAO Rongxiang. Preparation and oxidation desulfurization performance of Zirconium oxychloride based ternary deep eutectic solvent[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2023085
Citation: WANG Tianbo, LI Xiuping, ZHAO Rongxiang. Preparation and oxidation desulfurization performance of Zirconium oxychloride based ternary deep eutectic solvent[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2023085

氯氧化锆基三元低共熔溶剂的制备和氧化脱硫性能

doi: 10.19906/j.cnki.JFCT.2023085
基金项目: 辽宁省自然科学基金指导计划(2019-ZD-0064) 资助
详细信息
    通讯作者:

    E-mail: zylhzrx@126.com

  • 中图分类号: TQ028.8

Preparation and oxidation desulfurization performance of Zirconium oxychloride based ternary deep eutectic solvent

Funds: The project was supported by the Mentoring Program Projects from Liaoning Natural Science Foundation (2019-ZD-0064) .
  • 摘要: 通过简单加热乙二醇,对甲苯磺酸和八水氯氧化锆混合物制备了三元低共熔溶剂。采用傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1H NMR)验证了低共熔溶剂成功合成。分别采用紫外-可见吸收光谱和旋转式黏度计对其酸性和黏度进行测试。以双氧水作为氧化剂,以合成的低共熔溶剂为萃取剂和催化剂构成萃取-氧化脱硫系统,考察了低共熔溶剂的组成、反应温度、氧硫比、剂油比以及不同硫化物等对脱硫率的影响。实验结果表明,在氯氧化锆、乙二醇和对苯甲磺酸物质的量比为1∶10∶10,反应温度50 ℃、剂油比为1∶5、氧硫比为8的最佳反应条件下,二苯并噻吩(DBT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)、苯并噻吩(BT)模拟油的脱硫率分别为100%、92.2%、60%,且低共熔溶剂重复使用五次后脱硫率仍可达到96.2%,最后对氧化脱硫的机理进行了探讨。
  • 图  1  低共熔溶剂的合成过程

    Figure  1  Synthesis process of deep eutectic solvent

    图  2  DESs及其组成成分

    Figure  2  DESs and their composition

    图  3  不同低共熔溶剂的脱硫性能

    Figure  3  Desulfurization performance of different deep eutectic solvent

    Experimental conditions: V (DES) = 1 mL, n(ZOC)/n(TsOH)/n(EG)=1∶10∶10, Voil=5 mL, O/S=8, 50 ℃, 200 min.

    图  4  4-硝基二苯胺在不同DESs存在下的紫外-可见光谱谱图

    Figure  4  Ultraviolet visible spectra of 4-nitro diphenylamine in the presence of various DESs

    图  5  不同DESs的黏度

    Figure  5  Viscosities of Different DESs

    图  6  低共熔溶剂及其成分的红外光谱谱图

    Figure  6  Infrared spectra of deep eutectic solvents and their components

    图  7  低共熔溶剂及其成分的核磁共振谱图

    Figure  7  Nuclear magnetic resonance spectrum of deep eutectic solvent and their components

    图  8  低共熔溶剂酸性对脱硫效率的影响

    Figure  8  Influence of the acidity of deep eutectic solvents on desulfurization efficiency

    Reaction conditions: VDESs/Voil=1:5, O/S=8, 50 ℃, 200 min.

    图  9  ZOC/TsOH/EG物质的量比对脱硫效率的影响

    Figure  9  Effect of molar ratio of ethylene glycol to p-toluenesulfonic acid on Desulfurization rate

    Reaction conditions: VDESs/Voil=1:5, O/S=8, 50 ℃, 200 min.

    图  10  反应温度对脱硫效率的影响

    Figure  10  Effect of reaction temperature on desulfurization rate

    Reaction conditions: VDES/Voil=1:5, O/S=8, 200 min.

    图  11  氧硫比对脱硫效率的影响

    Figure  11  Effect of oxygen sulfur ratio on desulfurization rate

    Reaction conditions: VDESs/Voil=1:5, 50 ℃, 200 min.

    图  12  剂油比对脱硫效率的影响

    Figure  12  Effect of solvent oil ratio on desulfurization rate

    Reaction conditions: O/S=8, 50 ℃, 200 min.

    图  13  不同硫化物的脱除率

    Figure  13  Removal of on different sulfides

    Reaction conditions: VDESs/Voil = 1:5, O/S = 8, 50 ℃, 200 min.

    图  14  (a) EDSs回收对脱硫率的影响;(b) 反应前后DESs的红外光谱谱图

    Figure  14  (a) Effect of EDS recovery on desulfurization rate, (b) Infrared spectra of DESs before and after the reaction

    图  15  自由基捕获实验

    Figure  15  Free radical capture experiment

    图  16  DBT在油-DESs-H2O2体系中的萃取和催化氧化过程

    Figure  16  Extraction and catalytic oxidation process of DBT in the oil-DESs-H2O2 system

    表  1  低共熔溶剂酸度的参数

    Table  1  Parameters of acidity of deep eutectic solvents

    EntrySubstanceAmaxI(HI)+H0
    14-nitrodiphenylamine4.891000
    2TsOH4.4991.68.41.04
    3ZOC/TsOH/EG4.5793.46.41.16
    4TsOH/ZOC4.5192.27.81.07
    5TsOH/EG4.4390.59.50.98
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  • 收稿日期:  2023-10-24
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