咪唑类离子液体混合物用于二氧化硫高效吸收

doi:10.11949/0438-1157.20200790

化工学报 ›› 2020, Vol. 71 ›› Issue (11): 5035-5042.DOI: 10.11949/0438-1157.20200790

• 南京大学化工学院院庆专栏 • 上一篇下一篇

咪唑类离子液体混合物用于二氧化硫高效吸收

张雅婷¹(),熊文杰¹(),赵天翔^2,³,姚晨飞¹,丁宇宬¹,张效敏¹(),吴有庭¹,胡兴邦¹()

^1.南京大学化学化工学院，江苏南京 210023
^2.贵州大学化学与化工学院，贵州贵阳 550025
^3.贵州大学绿色化工与清洁能源技术重点实验室，贵州贵阳 550025

收稿日期:2020-06-22 修回日期:2020-09-11 出版日期:2020-11-05 发布日期:2020-11-05
通讯作者: 张效敏,胡兴邦
作者简介:张雅婷（1998—），女，硕士研究生，1640560372@qq.com|熊文杰（1996—），男，博士研究生，wenjie.xiong@outlook.com
基金资助:
国家自然科学基金项目(21676134);贵州大学自然科学专项基金(X2019065)

High capacity absorption of SO₂ using imidazole ionic liquid mixtures

Yating ZHANG¹(),Wenjie XIONG¹(),Tianxiang ZHAO^2,³,Chenfei YAO¹,Yucheng DING¹,Xiaomin ZHANG¹(),Youting WU¹,Xingbang HU¹()

^1.School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, Jiangsu, China
^2.School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, Guizhou, China
^3.Key Laboratory of Green Chemical and Clean Energy Technology, Guizhou University, Guiyang 550025, Guizhou, China

Received:2020-06-22 Revised:2020-09-11 Online:2020-11-05 Published:2020-11-05
Contact: Xiaomin ZHANG,Xingbang HU

摘要/Abstract

摘要：

开发易制备、价格便宜、面向SO₂气体高效分离的离子液体（ILs），是当前ILs从实验探索迈向工业应用的难点与重大挑战。合成了不同摩尔比（3∶1、2∶1、1∶1、1∶2和1∶3）的1-乙基-3-甲基咪唑氯盐（[Emim][Cl]）和1-乙基-3-甲基咪唑乙酸盐（[Emim][OAc]）的离子液体混合物[Emim][Cl]_x[OAc]_1-_x，在测定其密度、黏度、热稳定性等基本物性数据的基础上，研究了[Emim][Cl]_x[OAc]_1-_x混合物在不同温度和SO₂分压下的SO₂吸收能力。结果表明，[Emim][Cl]_x[OAc]_1-_x能够有效地捕获SO₂。[Emim][Cl]与[Emim][OAc]之间存在协同促进作用，有利于实现SO₂高效吸收。[Emim][Cl]_0.33[OAc]_0.66混合液在1.0和0.2 atm（1 atm=101325 Pa）下捕获SO₂量分别为（1.34±0.08）和（0.74±0.05） g/g，与现有结果相比，混合物在SO₂捕获方面有明显优势。此外，这些离子液体混合物对二氧化硫的吸收和解吸具有良好的可逆性。

关键词: 离子液体, 物理性质, 吸收, 二氧化硫, 解吸

Abstract:

The capture of sulfur dioxide (SO₂) with readily available and cost-effective ionic liquids (ILs) is one of the challenges for the application of ILs. Here, we synthesized the ILs mixtures with different molar ratios (3∶1, 2∶1, 1∶1, 1∶2, and 3∶1) of 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]) and 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) to study their SO₂ absorption capacities. The SO₂ solubilities in these mixtures were investigated under different conditions. The SO₂ absorption capacities of [Emim][Cl]_x[OAc]_1-_x at different temperatures and SO₂ partial pressure were measured. The results show that ILs can effectively capture SO₂. There exists a synergistic promotion effect between [Emim][Cl] and [Emim][OAc], resulting in quite high SO₂ absorption capacity. The [Emim][Cl]_0.33[OAc]_0.66 mixture can capture SO₂ (1.34±0.08) and (0.74±0.05) g/g at 1.0 and 0.2 atm(1 atm=101325 Pa), respectively. Comparing with the reported data, [Emim][Cl]_x[OAc]_1-_x mixtures show obvious advantage for SO₂ capture. In addition, these ionic liquid mixtures have good reversibility for the absorption and desorption of sulfur dioxide.

Key words: ionic liquids, physical property, absorption, sulfur dioxide, desorption

中图分类号:

O 69

张雅婷,熊文杰,赵天翔,姚晨飞,丁宇宬,张效敏,吴有庭,胡兴邦. 咪唑类离子液体混合物用于二氧化硫高效吸收[J]. 化工学报, 2020, 71(11): 5035-5042.

Yating ZHANG,Wenjie XIONG,Tianxiang ZHAO,Chenfei YAO,Yucheng DING,Xiaomin ZHANG,Youting WU,Xingbang HU. High capacity absorption of SO₂ using imidazole ionic liquid mixtures[J]. CIESC Journal, 2020, 71(11): 5035-5042.

图/表 12

图1 离子液体及其混合物在不同温度下的密度

Fig.1 Density of IL mixtures at different temperature

图2 离子液体及其混合物在不同温度下的黏度

Fig.2 Viscosity of IL mixtures at different temperature

表1 密度-温度和黏度-温度模型参数

Table 1 Density-temperature and viscosity-temperature model parameters

离子液体	ρ - T			η - T
离子液体	A	B	R²	a	b	c	R²
[Emim][OAc]	1.124	-6.16×10^-4	0.9989	73.35	-0.34	4.58×10^-4	0.9992
[Emim][Cl]_0.75[OAc]_0.25	1.151	-5.94×10^-4	0.9999	83.00	-0.44	5.97×10^-4	0.9978
[Emim][Cl]_0.66[OAc]_0.33	1.145	-5.93×10^-4	0.9999	65.79	-0.34	4.60×10^-4	0.9999
[Emim][Cl]_0.5[OAc]_0.5	1.140	-6.06×10^-4	0.9998	64.66	-0.40	5.51×10^-5	0.9999
[Emim][Cl]_0.33[OAc]_0.66	1.334	-6.12×10^-4	0.9999	78.22	-0.42	5.89×10^-6	0.9992
[Emim][Cl]_0.25[OAc]_0.75	1.133	-6.09×10^-4	0.9999	69.07	-0.37	5.06×10^-4	0.9998

图3 离子液体及其混合物的热稳定性

Fig.3 The thermal stability of IL and IL mixtures

图4 离子液体及其混合物在293.2 K和1.0 atm下吸收SO2的时间函数

Fig.4 SO2 absorption by IL mixtures as a function of time at 293.2 K and 1.0 atm

表2 不同体系对二氧化硫的吸收能力

Table 2 SO2 absorption capacities of different systems

ILs	SO₂absorption at 20℃/(g/g)	Ref.
[Emim][Cl]_0.75[OAc]_0.25	1.32±0.08	this work
[Emim][Cl]_0.66[OAc]_0.33	1.33±0.08	this work
[Emim][Cl]_0.5[OAc]_0.5	1.20±0.07	this work
[Emim][Cl]_0.33[OAc]_0.66	1.34±0.08	this work
[DMDEEH][MOAc]	1.02	[9]
[DMDEEH][EOAc]	1.06	[9]
[DMDEEH][MEAAc]	1.04	[9]
[EDBEAH][MOAc]	0.34	[9]
[TMPDAH][BAc]	1.23	[9]
EminCl-AA(2∶1)	1.39	[10]
[NH₂Emim][OAc]-[Bmim][OH] (1∶1)	0.36^①	[11]
[N₂₂₂₂][FA]/PEG₂₀₀	0.46^②	[12]
[Ch][FA]/PEG₂₀₀	0.30^②	[12]
[TMG][SUC]	0.88^①	[16]
[TMG][SUB]	0.95	[16]
[TMG][DOD]	0.83	[16]
[Emim][SCN]	1.13	[18]
[Emim][C(CN)₃]	0.74	[18]
[Emim][Cl]	1.20^③	[20]
[C₄Py][SCN]	0.44	[21]
[C₄Py][BF⁴]	0.84	[21]
[Emim][Cl][SCN](1∶1)	1.22	[22]
ChCl-EG (1∶2)	0.70	[23]
ChCl-thiourea (1∶1)	0.88	[23]

图5 温度对 [Emim][Cl][OAc]吸收SO2的影响 (1.0 atm)

Fig.5 Effect of temperature on SO2 absorption in [Emim][Cl][OAc] at 1.0 atm

图6 压力对[Emim][Cl][OAc] 吸收SO2的影响 (293.2 K)

Fig.6 Effect of pressure on SO2 absorption in [Emim][Cl][OAc] at 293.2 K

图7 313 K时低分压SO2在[Emim][Cl]0.66[OAc]0.33中的溶解度

Fig.7 SO2 absorption in [Emim][Cl]0.66[OAc]0.33 under low partial pressure at 313 K

图8 [Emim][Cl]0.66[OAc]0.33和[Emim][Cl]0.33[OAc]0.66的SO2吸收-解吸循环

Fig.8 SO2 absorption-desorption cycles in [Emim][Cl]0.66[OAc]0.33 and [Emim][Cl]0.33[OAc]0.66

图9 [Emim][Cl]0.66[OAc]0.33吸收SO2前后的红外光谱

Fig.9 FTIR spectrum for [Emim][Cl]0.66[OAc]0.33 before and after SO2 absorption

图10 [Emim][Cl][OAc]吸收SO2前后的1H NMR(a)和13C NMR(b)

Fig.10 1H NMR(a) and 13C NMR(b) of [Emim][Cl][OAc] before and after SO2 absorption

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咪唑类离子液体混合物用于二氧化硫高效吸收

High capacity absorption of SO₂ using imidazole ionic liquid mixtures

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咪唑类离子液体混合物用于二氧化硫高效吸收

High capacity absorption of SO2 using imidazole ionic liquid mixtures

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High capacity absorption of SO₂ using imidazole ionic liquid mixtures