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Title
Preparation and oxidation desulfurization performance of zirconium oxychloride based ternary deep eutectic solvent
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作者
王添渤李秀萍赵荣祥
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Author
WANG Tianbo;LI Xiuping;ZHAO Rongxiang
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单位
辽宁石油化工大学石油化工学院
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Organization
School of Petrochemical Engineering, Liaoning Petrochemical University
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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。
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Abstract
A zirconium oxychloride based ternary deep eutectic solvent (DES) was prepared by simply heating mixture of ethylene glycol, p-toluenesulfonic acid and octahydrate zirconium oxychloride. The successful synthesis of deep eutectic solvents was verified using Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy (1H NMR). The acidity and viscosity were tested using UV-visible absorption spectroscopy and rotary viscometer, respectively. The extraction-oxidation desulfurization system was composed of hydrogen peroxide as the oxidant, deep eutectic solvent as the extractant and catalyst. The effects of the composition of the deep eutectic solvent, reaction temperature, oxygen sulfur ratio, solvent oil ratio, and different sulfides on the desulfurization rate were investigated. The experimental results showed that the desulfurization rates of dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT), and benzothiophene (BT) simulated oil were 100%, 92.2%, and 60%, respectively, under the optimal reaction conditions of a molar ratio of 1:10:10 between zirconium oxychloride, ethylene glycol, and p-benzenesulfonic acid components, 50 ℃, a solvent oil ratio of 1∶5, and an oxygen sulfur ratio of 8. After repeated use of the deep eutectic solvent for 5 times, the desulfurization rate could still reach 96.2%. The mechanism of oxidative desulfurization was explored.
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关键词
低共熔溶剂氧化脱硫二苯并噻吩氯氧化锆
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KeyWords
deep eutectic solvent;oxidative desulfurization;DBT;zirconium oxychloride
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基金项目(Foundation)
辽宁省自然科学基金指导计划(2019-ZD-0064) 资助
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DOI
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引用格式
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）, 2024, 52(5): 647-655.
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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, 2024, 52(5): 647-655.
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相关文章
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图表
Table1
表 1 低共熔溶剂酸度的参数
| Entry | Substance | Amax | I | (HI)+ | H0 |
| 1 | 4-nitrodiphenylamine | 4.89 | 100 | 0 | − |
| 2 | TsOH | 4.49 | 91.6 | 8.4 | 1.04 |
| 3 | ZOC/TsOH/EG | 4.57 | 93.4 | 6.4 | 1.16 |
| 4 | TsOH/ZOC | 4.51 | 92.2 | 7.8 | 1.07 |
| 5 | TsOH/EG | 4.43 | 90.5 | 9.5 | 0.98 |
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燃料化学学报(中英文) 
2024年第05期 
