Preparation and oxidation desulfurization performance of zirconium oxychloride based ternary deep eutectic solvent
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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。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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Key words:
- deep eutectic solvent /
- oxidative desulfurization /
- DBT /
- zirconium oxychloride
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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 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 spectra 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 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
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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