咪唑类三元低共熔溶剂捕集低压SO2的实验研究

doi:10.11949/0438-1157.20191266

摘要/Abstract

摘要：

近几年来，以氢键受体（HBA）和氢键供体（HBD）组成的低共熔溶剂（DESs）以其类似于离子液体的性质被认为是一种有潜力的SO₂吸附剂。为制备用于低压SO₂吸收的容量大、价格合理、循环性能好的低共熔溶剂，选用咪唑(Im)作为功能化组分，以价格低廉的甘油(Gly)、PEG200和乙二醇(EG)作为第二HBD，与作为HBA的氯化胆碱(CC)构建CC-GIy-Im、CC-PEG200-Im、CC-EG-Im三元功能化低共熔溶剂，并用于低压SO₂的捕集实验研究。着重考察了第二HBD种类、咪唑含量、温度等因素对DESs吸收SO₂的性能影响。结果表明：在所选的第二HBD中，PEG200的性能最佳，其构建的低共熔溶剂密度、黏度适中，热稳定性好，吸收性好；CC-PEG200-Im（1∶2∶7）在40℃下，对1% SO₂的吸收量达到0.236 g SO₂/g DES；经5次吸收-解吸循环后，低共熔溶剂吸收性能仍然稳定；¹H NMR谱图分析结果表明，CC-PEG200-Im对SO₂的吸收机理为化学吸收。

关键词: 二氧化硫, 低共熔溶剂, 吸收, 功能化

Abstract:

In recent years, DESs, which is composed of hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD), is considered as a potential SO₂ adsorbent due to its properties similar to ionic liquids. To prepare the DESs with large absorption capacity for low pressure SO₂, reasonable price and good recycling performance, three ternary functionalized DESs of CC-Gly-Im, CC-PEG200-Im, CC-EG-Im were developed using choline chloride (CC) as HBA, imidazole (Im) as functional component, and cheap glycerol (Gly), PEG200, ethylene glycol (EG) as second HBD. The obtained DESs were further applied for experimental study for low pressure SO₂, focusing on the type of second HBD, the content of imidazole, and temperature on the absorption performance of SO₂. The results showed that PEG200 demonstrated the best property, and its DESs possessed moderate density and viscosity, satisfactory thermal stability and absorption capacity. The maximum absorption of CC-PEG200-Im (1∶2∶7) DESs for 1% SO₂at 40℃ reached 0.236 g SO₂/g DES. The DESs presented stable absorption performance for SO₂ after five absorption-desorption cycles. The CC-PEG200-Im could absorb SO₂ by chemical interactions at the experimental conditions under ¹H NMR spectrum investigation.

Key words: sulfur dioxide, deep eutectic solvent, absorption, functionalized

中图分类号:

TQ 028.8

邓晓霞, 龚磊, 刘小棒, 邓东顺. 咪唑类三元低共熔溶剂捕集低压SO₂的实验研究[J]. 化工学报, 2020, 71(1): 368-375.

Xiaoxia DENG, Lei GONG, Xiaobang LIU, Dongshun DENG. Study on the capture of low pressure SO₂ by imidazole-based ternary deep eutectic solvents[J]. CIESC Journal, 2020, 71(1): 368-375.

图/表 11

图1 三种DESs密度随温度的变化

Fig.1 Density of three DESs at different temperatures

图2 三种DESs黏度随温度的变化

Fig.2 Viscosity of three DESs at different temperatures

图3 三种DESs的热失重

Fig.3 TGA curves of three DESs

图4 40℃下三种DES对1%SO2的吸收

Fig.4 Absorption profiles of three DESs at 40℃ for 1%SO2

图5 40℃下不同比例的CC-PEG200-Im DESs对1%SO2的吸收曲线

Fig.5 Absorption profiles of CC-PEG200-Im DESs with various proportion at 40℃ for 1%SO2

图6 40℃下不同比例的CC-PEG200-Im DESs对0.33%SO2的吸收曲线

Fig.6 Absorption profiles of CC-PEG200-Im DESs with various proportion at 40℃ for 0.33% SO2

图7 不同温度下CC-PEG200-Im (1∶2∶3) DESs对1% SO2的吸收曲线

Fig.7 Absorption profiles of CC-PEG200-Im (1∶2∶3) DESs for 1%SO2 at different temperatures

表1 低SO2压力下本文的DESs与文献中DESs的吸收容量比较

Table 1 Comparison of absorption capacity between present DESs and other DESs from literatures under low pressure SO2

DESs (摩尔比)	温度/℃	SO₂浓度或分压	吸收容量/ (g SO₂/g DES)	文献
CC-PEG200-Im (1∶2∶7)	40	1%	0.236	本研究
CC-PEG200-Im (1∶2∶5)	40	0.33%	0.140	本研究
CC-Gly (1∶1)	20	0.01 MPa	0.153	[10]
CC-EG (1∶2)	30	0.02 MPa	0.158	[12]
Im-Gly (1∶2)	40	0.2%	0.161	[15]
乙烯脲- 1-丁基-3-甲基咪唑氯盐 (1∶2)	20	2%	0.250	[25]
L-卡尼丁-EG (1∶3)	40	2%	0.151	[26]
L-卡尼丁-EG (1∶3)	40	0.37%	0.119	[26]
1-乙基-3-甲基咪唑氯盐-丁二腈 (1∶1)	20	0.2%	0.120	[27]
1-丁基-3-甲基咪唑氯盐-4-甲基咪唑 (1∶2)	20	0.1%	0.189	[28]

图8 CC-PEG200-Im (1∶2∶3) 5次连续循环吸收-解吸循环结果

Fig.8 SO2 absorption and desorption by CC-PEG200-Im (1∶2∶3) for 5 cycles

图9 CC-PEG200-Im (1∶2∶3)吸收SO2前后的核磁氢谱图

Fig.9 1H NMR spectra of fresh and SO2-saturated CC-PEG200-Im (1∶2∶3)

图10 CC-PEG200-Im (1∶2∶3)和SO2之间的吸收机制

Fig.10 Proposed chemical mechanism between CC-PEG200-Im (1∶2∶3) and SO2

参考文献 28

1	周静雪, 李智, 宁原峰, 等 . 含氰基离子液体的物理性能及其对SO₂的吸收性能[J/OL]. 应用化工, 2019. https://doi.org/10.16581/j.cnki.issn1671-3206.20190729.042.
	Zhou J X , Li Z , Ning Y F , et al . Physical properties of cyano-containing ionic liquids and their absorption properties for SO₂ [J/OL]. Applied Chemical Industry, 2019. https: //doi.org/10.16581/j.cnki.issn1671-3206.20190729.042.
2	梁昌娟, 李红海 . 离子液体[BMIM]OH对SO₂的吸收性能[J]. 化学工业与工程, 2019, 36(4): 18-22.
	Liang C J , Li H H . Absorption of SO₂ by ionic liquid [BMIM]OH[J]. Chemical Industry and Engineering, 2019, 36(4): 18-22.
3	崔国凯, 赵宁, 张峰涛, 等 . 离子液体捕集二氧化硫气体的研究进展[J]. 科学通报, 2016, 61(28): 3115-3126.
	Cui G K , Zhao N , Zhang F T , et al . Progress in SO₂ capture by ionic liquids [J]. Chinese Science Bulletin, 2016, 61(28): 3115-3126.
4	Ma X X , Kaneko T , Tashimo T , et al . Use of limestone for SO₂ removal from flue gas in the semidry FGD process with a powder-particle spouted bed[J]. Chemical Engineering Science, 2000, 55: 4643-4652.
5	窦金孝, 赵永奇, 段晓谞, 等 . 络合亚铁乙二醇-四丁基溴化铵低共熔溶剂协同吸收SO₂和NO[J/OL]. 化工进展, 2019. http: //kns.cnki.net/kcms/detail/11.1954.tq.20190808.1451.038.html.
	Dou J X , Zhao Y Q , Duan X X , et al . Co-adsorption of SO₂ and NO from flue gas using Fe(II) EG-TBAB deep eutectic solvents[J/OL]. Chemical Industry and Engineering Progress, 2019. http: //kns.cnki.net/kcms/detail/11.1954.tq.20190808.1451.038.html.
6	Deng D S , Liu X B , Gao B . Physicochemical properties and investigation of azole-based deep eutectic solvents as efficient and reversible SO₂ absorbents[J]. Industrial & Engineering Chemistry Research, 2017, 56: 13850-13856.
7	Huang K , Wang G N , Dai Y , et al . Dicarboxylic acid salts as task-specific ionic liquids for reversible absorption of SO₂ with a low enthalpy change[J]. RSC Advances, 2013, 3: 16264-16269.
8	Wang C M , Cui G K , Luo X Y , et al . Highly efficient and reversible SO₂ capture by tunable azole-based ionic liquids through multiple-site chemical absorption [J]. Journal of the American Chemical Society, 2011, 133: 11916-11919.
9	Wu W Z , Han B X , Gao H X , et al . Desulfurization of flue gas: SO₂ absorption by an ionic liquid [J]. Angewandte Chemie, International Edition, 2004, 43: 2415-2417.
10	Yang D Z , Hou M Q , Ning H , et al . Efficient SO₂ absorption by renewable choline chloride-glycerol deep eutectic solvents[J]. Green Chemistry, 2013, 15: 2261.
11	Liu B Y , Wei F X , Zhao J J , et al . Characterization of amide-thiocyanates eutectic ionic liquids and their application in SO₂ absorption[J]. RSC Advances, 2013, 3: 2470-2476.
12	Sun S Y , Niu Y X , Xu Q , et al . Efficient SO₂ absorption by four kinds of deep eutectic solvents based on choline chloride[J]. Industrial & Engineering Chemistry Research, 2015, 54: 8019-8024.
13	Yang D Z , Han Y , Qi H , et al . Efficient absorption of SO₂ by EmimCl-EG deep eutectic solvents[J]. ACS Sustainable Chemistry & Engineering, 2017, 5: 6382-6386.
14	Yang D Z , Zhang S Z , Jiang D E , et al . SO₂ absorption in EmimCl-TEG deep eutectic solvents[J]. Physical Chemistry Chemical Physics, 2018, 20: 15168.
15	Zhang K , Ren S H , Yang X , et al . Efficient absorption of low-concentration SO₂ in simulated flue gas by functional deep eutectic solvents based on imidazole and its derivatives[J]. Chemical Engineering Journal, 2017, 327: 128-134.
16	Tian S D , Hou Y C , Wu W Z , et al . Hydrophobic task-specific ionic liquids: synthesis, properties and application for the capture of SO₂ [J]. Journal of Hazardous Materials, 2014, 278: 409-416.
17	刘小棒 . 功能化低共熔溶剂用于SO₂捕集的实验研究[D]. 杭州: 浙江工业大学, 2018.
	Liu X B . Experimental investigation of the functionalized deep eutectic solvents for capturing SO₂ [D]. Hangzhou: Zhejiang University of Technology, 2018.
18	Zhu J H , Xu Y J , Feng X , et al . A detailed study of physicochemical properties and microstructure of EmimCl-EG deep eutectic solvents: their influence on SO₂ absorption behavior[J]. Journal of Industrial and Engineering Chemistry, 2018, 67: 148-155.
19	Chai M Y , Zhao W B , Li J M . Novel SO₂ phase-change absorbent: mixture of N, N-dimethylaniline and liquid paraffin[J]. Industrial & Engineering Chemistry Research, 2018, 57: 12502-12510.
20	Han G Q , Jiang Y T , Deng D S , et al . Solubilities and thermodynamic properties of SO₂ in five biobased solvents[J]. Chemical Thermodynamics, 2016, 92: 207-213.
21	Zhao T X , Liang J , Wu Y T , et al . Unexpectedly efficient SO₂ capture and conversion to sulfur in novel imidazole-based deep eutectic solvents[J]. Chemical Communications, 2018, 54: 8964.
22	Liu X B , Gao B , Jiang Y T , et al .Solubilities and thermodynamic properties of carbon dioxide in guaiacol-based deep eutectic solvents[J]. Journal of Chemical & Engineering Data, 2017, 62: 1448-1455.
23	何志强, 鄢浩, 王骑虎, 等 . 温度对氯化胆碱／多元醇型低共熔溶剂物性的影响[J]. 上海大学学报, 2015, 21: 384-392.
	He Z Q , Yan H , Wang Q H , et al . Effect of temperature on physic-chemical properties of deep eutectic solvent based on choline chloride and polyols[J]. Journal of Shanghai University, 2015, 21: 384-392.
24	陈玲, 赵倩, 汪洋, 等 . 离子液体中阴阳离子的特性对其吸收二氧化硫的影响[J]. 材料导报, 2018, 32: 2949-2958.
	Chen L , Zhao Q , Wang Y , et al . Effect of anionic and cationic characteristic on the SO₂ absorption performance of ionic liquids[J]. Materials Reports, 2018, 32: 2949-2958.
25	Jiang B , Zhang H M , Zhang L H , et al . Novel deep eutectic solvents for highly efficient and reversible absorption of SO₂ by preorganization strategy[J]. ACS Sustainable Chemistry & Engineering, 2019, 7: 8347-8357.
26	Zhang K , Ren S H , Hou Y C , et al . Efficient absorption of SO₂ with low-partial pressures by environmentally benign functional deep eutectic solvents[J]. Journal of Hazardous Materials, 2017, 324: 457-463.
27	Yang D Z , Zhang S Z , Jiang D E . Efficient absorption of SO₂ by deep eutectic solvents formed by biobased aprotic organic compound succinonitrile and 1-ethyl-3-methylimidazolium chloride[J]. ACS Sustainable Chemistry & Engineering, 2019, 7: 9086-9091.
28	Yang C , Jiang B , Dou H Z , et al . Highly efficient and reversible capture of low partial pressure SO₂ by functional deep eutectic solvents[J]. Energy Fuels, 2018, 32: 10737-10744.

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咪唑类三元低共熔溶剂捕集低压SO₂的实验研究

Study on the capture of low pressure SO₂ by imidazole-based ternary deep eutectic solvents

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