EMIES/nC9H10O2基低共熔溶剂的制备及其氧化脱硫活性的研究

doi:10.11949/j.issn.0438-1157.20181251

摘要/Abstract

摘要：

通过简单加热1-乙基-3-甲基咪唑硫酸乙酯（EMIES）离子液体和3-苯丙酸（C₉H₁₀O₂）的混合物，制备了一系列酸性低共熔溶剂EMIES/nC₉H₁₀O₂（n=0.25,0.5,1,2,4）。通过FTIR，¹H NMR和TGA的表征，确定EMIES/nC₉H₁₀O₂的结构。以该低共熔溶剂为催化剂和萃取剂，H₂O₂为氧化剂，组成氧化-萃取脱硫体系，用于脱除模拟油中的硫化物。考察了原料配比、反应温度、氧硫比（O/S）、低共熔溶剂加入量和不同硫化物对脱硫性能的影响。结果表明，在EMIES和C₉H₁₀O₂摩尔比为1∶1，反应温度为50℃，O/S比为8，低共熔溶剂加入量为1.5 g和模拟油5 ml的反应条件下，二苯并噻吩、4,6-二甲基二苯并噻吩和苯并噻吩的脱除率分别为94.8%、91.6%和46.4%。低共熔溶剂可循环使用6次，活性无明显下降。此外，对该氧化-萃取脱硫体系的脱硫机理进行了探讨。

关键词: 溶剂萃取, 回收, 催化剂, 低共熔溶剂

Abstract:

A series of acidic deep eutectic solvents (DESs) EMIES/nC₉H₁₀O₂（n=0.25, 0.5, 1, 2, 4） were synthesized by simply heating the mixture of 1-ethyl-3-methylimidazolium ethylsulfate (EMIES) and 3-phenylpropionic acid (C₉H₁₀O₂). The structure of EMIES/nC₉H₁₀O₂ was determined by FTIR, ¹H NMR and TGA characterization. The extraction-oxidation desulfurization system was developed to remove sulfides from model oil using EMIES/nC₉H₁₀O₂ as the extractant and catalyst, H₂O₂ as the oxidation. The influences of raw material ratio, reaction temperature, O/S ratio, amount of DESs and different sulfide on the desulfurization performance were investigated. The experimental results demonstrated the optimal reaction conditions were molar ratio of EMIES to C₉H₁₀O₂ of 1∶1, temperature of 50℃, O/S ratio of 8, the amount of DESs of 1.5 g and 5 ml model oil. Removal rate of DBT, 4, 6-DMDBT and BT reached 94.8%, 91.6% and 46.4%, respectively, under the optimal condition. The DESs can be reused for 6 times without significant decrease in activity. In addition, the desulfurization mechanism of the oxidation-extraction desulfurization system was discussed.

Key words: solvent extraction, recovery, catalysis, deep eutectic solvents

中图分类号:

TE 624

王鑫博, 张延平, 李秀萍, 赵荣祥. EMIES/nC₉H₁₀O₂基低共熔溶剂的制备及其氧化脱硫活性的研究[J]. 化工学报, 2019, 70(4): 1567-1574.

Xinbo WANG, Yanping ZHANG, Xiuping LI, Rongxiang ZHAO. Preparation of EMIES/nC₉H₁₀O₂-based deep eutectic solvents and its oxidative desulfurization activity[J]. CIESC Journal, 2019, 70(4): 1567-1574.

图/表 13

图1 低共熔溶剂的合成过程

Fig.1 Synthesis process of deep eutectic solvents

图2 低共熔溶剂的FTIR谱图

Fig.2 FTIR spectra of DESs

图3 低共熔溶剂的 1H NMR谱图

Fig.3 1H NMR spectra of DESs

图4 EMIES/C9H10O2低共熔溶剂的热重分析曲线

Fig.4 TGA curves of EMIES/C9H10O2

图5 1-乙基-3-甲基咪唑硫酸乙酯与3-苯丙酸摩尔比对脱硫率的影响

Fig.5 Influence of different molar ratio of EMIES to C9H10O2 on desulfurization rate(Reaction condition:V oil= 5 ml, n(H2O2)/n(S)= 8, 1.5 g DESs, 50℃)

图6 反应温度对脱硫率的影响

Fig.6 Influence of reaction temperature on desulfurization rate

表1 氧硫比对脱硫率的影响

Table 1 Influence of various O/S molar ratio on desulfurization rate

O/S	Sulfur removal/%
0	20.4
2	40.2
4	46.2
6	86.4
8	94.8
10	95.1

表2 低共熔溶剂的量对脱硫率的影响

Table 2 Influence of amount of DESs on desulfurization rate

Amount of DESs/g	Sulfur removal/%
0.5	74.0
1.0	83.0
1.5	94.8
2.0	93.2

图7 不同硫化物的脱除性能

Fig.7 Removal performance of different sulfides

图8 脱除不同硫化物的动力学分析

Fig.8 Kinetic analysis of removal of different sulfides

表3 低共熔溶剂的回收对脱硫率的影响

Table 3 Influence of DESs recycling on sulfur removal

Recyling times	Sulfur removal/%
1	94.8
2	94.0
3	92.6
4	92.0
5	90.2
6	89.3

图9 DBT和氧化产物的红外光谱

Fig.9 FTIR spectra of DBT and oxidation products

图10 低共熔溶剂存在下氧化脱硫机理

Fig.10 Oxidative desulfurization mechanism in the presence of DESs

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EMIES/nC₉H₁₀O₂基低共熔溶剂的制备及其氧化脱硫活性的研究

Preparation of EMIES/nC₉H₁₀O₂-based deep eutectic solvents and its oxidative desulfurization activity

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