含醚阴离子功能化离子液体高效捕集SO2

doi:10.11949/0438-1157.20191261

摘要/Abstract

摘要：

发展高效、经济、绿色的SO₂吸收剂不但具有较强的学术价值，而且有良好的应用前景。设计并制备了一系列含醚的阴离子功能化离子液体，系统地研究了阴离子上引入醚基团对离子液体SO₂吸收容量的影响。结果表明，在阴离子的苯环上引入甲氧基，对离子液体的吸收容量有明显提升。当阳离子为摩尔质量更小的三丁基乙基磷[P₄₄₄₂]时，所得离子液体的吸收容量没有明显下降，20℃、10⁵ Pa SO₂下，[P₄₄₄₂][2-CH₃OPhCOO]有效吸收量为每摩尔离子液体吸收3.32 mol SO₂，有效质量吸收量是每克离子液体吸收0.56 g SO₂。六次吸收解吸循环，表明[P₄₄₄₂][2-CH₃OPhCOO]可以高效可逆地捕集SO₂。基于含醚阴离子功能化离子液体的加强效应进行气体捕集的方法，可进一步应用于分离、催化等领域。

关键词: SO₂, 甲氧基, 功能化, 离子液体, 气体捕集

Abstract:

The development of high efficient, economic and green SO₂ absorbers not only has a strong academic value, but also has a good application prospect. Herein, a series of ether-containing anion-functionalized ionic liquids were designed and prepared. The effect of ether on SO₂ absorption was investigated. The results indicated that SO₂ capacity increased significantly when ether was introduced on the anion. Furthermore, absorption capacity of SO₂ did not decrease obviously when the cation with a smaller molar mass tributyl ethyl phosphorus [P₄₄₄₂] was used. The effective absorption capacity of [P₄₄₄₂][2-CH₃OPhCOO] was 3.32 mol SO₂ per 1 mol IL at 20℃ and 10⁵ Pa, with the effective mass absorption of 0.56 g SO₂ per 1 g IL. The cycles of six absorption and desorption showed that SO₂ capture by [P₄₄₄₂][2-CH₃OPhCOO] was efficient and reversible. The method introducing ether to improve gas capture may be useful for other fields such as separation, catalyst and so on.

Key words: SO₂, methoxyl group, functional, ionic liquids, gas capture

中图分类号:

TQ 013.1

肖俏欣, 林文俊, 李浩然, 王从敏. 含醚阴离子功能化离子液体高效捕集SO₂[J]. 化工学报, 2020, 71(1): 361-367.

Qiaoxin XIAO, Wenjun LIN, Haoran LI, Congmin WANG. Efficient SO₂ capture by ether-containing anion-functionalized ionic liquids[J]. CIESC Journal, 2020, 71(1): 361-367.

图/表 13

图1 用于SO2吸收的离子液体的阴阳离子结构

Fig.1 Structures of cation and anion in anion-functionalized ionic liquids for SO2 capture

表1 含醚阴离子功能化的离子液体在105 Pa下的SO2吸收效果

Table 1 SO2 absorption of ionic liquid functionalized with ether anion at 105 Pa

离子液体	吸收量/(mol·mol^-1)	解吸残余量/(mol·mol^-1)	净吸收量/(mol·mol^-1)	吸收焓^①/(kJ·mol^-1)
[P₆₆₆₁₄][PhCOO]	3.56	0.51	3.05	-81.21
[P₆₆₆₁₄][3-CH₃OPhCOO]	4.29	0.51	3.78	-96.50
[P₆₆₆₁₄][2-CH₃OPhCOO]	4.49	0.56	3.93	-97.30
[P₆₆₆₁₄][4-CH₃OPhCOO]	4.22	0.53	3.69	-104.30
[P₄₄₄₂][PhCOO]	3.33	0.55	2.78	-81.21
[P₄₄₄₂][2-CH₃OPhCOO]	4.00	0.68	3.32	-97.30

图2 不同离子液体的SO2吸收和解吸

Fig.2 SO2 absorption and desorption by different ionic liquids

图3 不同离子液体对104 Pa SO2吸收和解吸

Fig.3 104 Pa SO2 absorption and desorption by different ionic liquids

图4 [P4442][2-CH3OPhCOO]、[P4442][PhCOO]对SO2吸收和解吸

Fig.4 SO2 absorption and desorption in [P4442][2-CH3OPhCOO] or [P4442][PhCOO]

图5 [P4442][2-CH3OPhCOO]、[P4442][ PhCOO]对104 Pa SO2吸收和解吸

Fig.5 104 Pa SO2 absorption and desorption in [P4442][2-CH3OPhCOO] or [P4442][PhCOO]

图6 压力对离子液体吸收SO2的影响

Fig.6 Effect of pressure on SO2 absorption

图7 温度对离子液体吸收SO2的影响

Fig.7 Effect of temperature on SO2 absorption

图8 [P4442][2-CH3OPhCOO]的SO2吸收循环实验

Fig.8 SO2 absorption by [P4442][2-CH3OPhCOO] for 6 cycles

图9 [P4442][PhCOO]、[P4442][2-CH3OPhCOO]吸收SO2的DFT计算（键长单位：10-10m）

Fig.9 DFT calculations of interaction between [P4442][PhCOO] or [P4442][2-CH3OPhCOO] with SO2 molecule

图10 [P4442][2-CH3OPhCOO]、[P4442][ PhCOO]吸收SO2前后的红外光谱 a—吸收SO2前的[P4442][PhCOO]；b—吸收SO2后的[P4442][PhCOO]; c—吸收SO2前的[P4442][2-CH3OPhCOO]；d—吸收SO2后的[P4442][2-CH3OPhCOO]

Fig.10 IR spectra of [P4442][2-CH3OPhCOO] or [P4442][ PhCOO]

图11 [P4442][2-CH3OPhCOO]、[P4442][ PhCOO]吸收SO2前后的1H NMR谱(溶剂氘代氯仿) a—吸收SO2前的[P4442][PhCOO]；b—吸收SO2后的[P4442][PhCOO]; c—吸收SO2前的[P4442][2-CH3OPhCOO]；d—吸收SO2后的[P4442][2-CH3OPhCOO]

Fig.11 1H NMR spectra of [P4442][2-CH3OPhCOO] or [P4442][PhCOO]

图12 [P4442][2-CH3OPhCOO]、[P4442][ PhCOO]吸收SO2前后的13C NMR谱(溶剂氘代氯仿) a—吸收SO2前的[P4442][PhCOO]；b—吸收SO2后的[P4442][PhCOO]; c—吸收SO2前的[P4442][2-CH3OPhCOO]；d—吸收SO2后的[P4442][2-CH3OPhCOO]

Fig.12 13C NMR spectra of [P4442][2-CH3OPhCOO] or [P4442][PhCOO]

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含醚阴离子功能化离子液体高效捕集SO₂

Efficient SO₂ capture by ether-containing anion-functionalized ionic liquids

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