三乙二醇二甲醚吸收低浓度SO2性能及机理研究

doi:10.11949/0438-1157.20200884

化工学报 ›› 2020, Vol. 71 ›› Issue (11): 5052-5058.DOI: 10.11949/0438-1157.20200884

• 南京大学化工学院院庆专栏 • 上一篇下一篇

三乙二醇二甲醚吸收低浓度SO₂性能及机理研究

杨小青^1,²(),廖泉飞^1,²,易芸^1,²,杨春亮^1,²,赵天翔^1,²(),胡兴邦³,刘飞^1,²

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

收稿日期:2020-07-03 修回日期:2020-08-16 出版日期:2020-11-05 发布日期:2020-11-05
通讯作者: 赵天翔
作者简介:杨小青（1996—），女，硕士研究生，chem409xqy@yeah.net
基金资助:
贵州大学自然科学专项基金项目(X2019065);贵州省科技创新人才团队项目(黔科合平台人才[2018]5607)

Study on performance and mechanism of triethylene glycol dimethyl ether for capturing low concentration SO₂

Xiaoqing YANG^1,²(),Quanfei LIAO^1,²,Yun YI^1,²,Chunliang YANG^1,²,Tianxiang ZHAO^1,²(),Xingbang HU³,Fei LIU^1,²

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

Received:2020-07-03 Revised:2020-08-16 Online:2020-11-05 Published:2020-11-05
Contact: Tianxiang ZHAO

摘要/Abstract

摘要：

多羟基醇如丙三醇、乙二醇、聚乙二醇等富含氢键位点，通过氢键相互作用能循环捕集SO₂气体。然而，羟基比例更高的丙三醇和乙二醇对SO₂的吸收能力远弱于聚乙二醇，这表明除氢键作用之外，可能还存在SO₂与醚氧原子间的电荷转移作用。为了证实SO₂与醚氧原子间的电荷转移作用，实验选择沸点较高的三乙二醇二甲醚作为SO₂的吸收剂。首先采用气体动态单循环法测定了低浓度SO₂（体积分数为2010 × 10^-6）在122.7 kPa和293.15~313.15 K下的汽液相平衡数据，并且基于汽液平衡数据，计算了SO₂吸收过程的热力学参数，包括亨利常数、熵变、焓变和Gibbs自由能等。此外，基于紫外光谱、红外光谱和核磁波谱的实验结果，证实了SO₂和三乙二醇二甲醚之间的O…S电荷转移相互作用。

关键词: 二氧化硫, 三乙二醇二甲醚, 吸收, 汽液平衡, 热力学, 机理研究

Abstract:

Polyhydric alcohols such as glycerol, ethylene glycol, polyethylene glycol, etc., are rich in hydrogen bonded sites and can trap SO₂ gas cyclically through hydrogen bond interactions. Although both glycerol and ethylene glycol have more hydroxyl groups than polyethylene glycol, the absorption capacity of SO₂ is lower than that of polyethylene glycol, which indicates that in addition to the hydrogen bonding effect, there may be a charge transfer effect between SO₂ and ether oxygen atoms of polyethylene glycol. Herein, to clarify the charge transfer effect between SO₂ and ether oxygen atoms, triethylene glycol dimethyl ether with a higher boiling point was selected as SO₂ absorbent. First, the gas-liquid equilibrium data of diluted SO₂ (2010 × 10^-6) at 122.7 kPa and 293.15 to 313.15 K were measured by a gas dynamic single cycle method. Then the thermodynamic parameters of the absorption process were calculated based on the SO₂ solubility data, including Henry??s constant, entropy change, enthalpy change and Gibbs free energy. In addition, the O…S charge transfer interaction between SO₂ and triethylene glycol dimethyl ether was confirmed by using UV-Vis, FTIR and NMR spectroscopy.

Key words: sulfur dioxide, triethylene glycol dimethyl ether, absorption, gas-liquid equilibrium, thermodynamics, mechanism study

中图分类号:

TQ 028.8

杨小青,廖泉飞,易芸,杨春亮,赵天翔,胡兴邦,刘飞. 三乙二醇二甲醚吸收低浓度SO₂性能及机理研究[J]. 化工学报, 2020, 71(11): 5052-5058.

Xiaoqing YANG,Quanfei LIAO,Yun YI,Chunliang YANG,Tianxiang ZHAO,Xingbang HU,Fei LIU. Study on performance and mechanism of triethylene glycol dimethyl ether for capturing low concentration SO₂[J]. CIESC Journal, 2020, 71(11): 5052-5058.

图/表 11

图1 汽液相平衡测定装置图1—吸收釜；2—冷阱；3—恒温槽；4—气体循环泵；5—气相色谱；6—三通阀；7—温度计；8— 压力传感器；9—SO2/N2混合气钢瓶；10—缓冲瓶；11—尾气吸收瓶；12—液体循环泵

Fig.1 Sketch of the experimental apparatus

表1 不同温度下三乙二醇二甲醚吸收低浓度SO2的汽液相平衡数据

Table 1 Gas-liquid equilibrium data for dilute SO2 in triethylene glycol dimethyl ether at different temperature

T/K	$C S O 2$ /(mol·m^-3)	$p S O 2$ /Pa	$y S O 2$ × 10⁶
293.15	6.83	16.5	134
	12.95	30.2	246
	18.05	40.8	333
	22.44	52.0	425
	31.31	70.7	577
	35.55	79.5	649
	45.19	101.9	832
298.15	8.87	25.5	208
	12.90	36.6	298
	17.85	49.7	406
	22.95	63.1	515
	29.12	80.6	658
	33.00	92.5	755
	37.59	106.3	867
303.15	1.91	13.6	111
	3.11	18.5	151
	6.42	31.2	254
	10.56	48.3	395
	14.90	63.8	521
	17.70	75.7	618
	25.77	105.0	857
308.15	2.74	13.1	107
	5.07	25.8	210
	7.14	36.2	295
	10.25	50.7	414
	14.23	70.5	576
	16.30	80.0	653
	21.37	106.1	866
313.15	1.45	10.9	89
	4.50	33.1	270
	7.14	49.3	403
	8.38	58.1	474
	10.82	71.2	581
	13.87	92.5	755
	15.06	100.2	818

表1 不同温度下三乙二醇二甲醚吸收低浓度SO2的汽液相平衡数据

Table 1 Gas-liquid equilibrium data for dilute SO2 in triethylene glycol dimethyl ether at different temperature

T/K	$C S O 2$ /(mol·m^-3)	$p S O 2$ /Pa	$y S O 2$ × 10⁶
293.15	6.83	16.5	134
	12.95	30.2	246
	18.05	40.8	333
	22.44	52.0	425
	31.31	70.7	577
	35.55	79.5	649
	45.19	101.9	832
298.15	8.87	25.5	208
	12.90	36.6	298
	17.85	49.7	406
	22.95	63.1	515
	29.12	80.6	658
	33.00	92.5	755
	37.59	106.3	867
303.15	1.91	13.6	111
	3.11	18.5	151
	6.42	31.2	254
	10.56	48.3	395
	14.90	63.8	521
	17.70	75.7	618
	25.77	105.0	857
308.15	2.74	13.1	107
	5.07	25.8	210
	7.14	36.2	295
	10.25	50.7	414
	14.23	70.5	576
	16.30	80.0	653
	21.37	106.1	866
313.15	1.45	10.9	89
	4.50	33.1	270
	7.14	49.3	403
	8.38	58.1	474
	10.82	71.2	581
	13.87	92.5	755
	15.06	100.2	818

图2 不同温度下三乙二醇二甲醚吸收低浓度SO2的汽液相平衡曲线

Fig.2 Gas-liquid equilibrium curves of dilute SO2 in triethylene glycol dimethyl ether at different temperature

图3 298.15 K下SO2为500 × 10-6时SO2在各种醇中的溶解度

Fig.3 Solubility of SO2 in various alcohols when SO2 is 500 × 10-6 at 298.15 K

图4 微量水分对三乙二醇二甲醚吸收低浓度SO2的影响

Fig.4 The effect of trace water on the absorption of dilute SO2 by triethylene glycol dimethyl ether

图5 三乙二醇二甲醚吸收低浓度SO2的lnHx与1/T拟合结果

Fig.5 Plot of lnHxvs 1/T of dilute SO2 in triethylene glycol dimethyl ether

表2 三乙二醇二甲醚吸收低浓度SO2气体的亨利常数、吸收焓变、吸收熵变和Gibbs自由能变

Table 2 Henry’s law constants, absorption enthalpy changes and entropy, and Gibbs free energy changes of dilute SO2 in triethylene glycol dimethyl ether

T/K	H_x/ (Pa·m³·mol^-1)	ΔH/ (kJ·mol^-1)	ΔS/ (J·mol^-1·K^-1)	ΔG/ (kJ·mol^-1)
293.15	2.22 ± 0.05	-37.16	-74.08	-15.45
298.15	2.80 ± 0.03			-15.08
303.15	3.84 ± 0.04			-14.71
308.15	4.96 ± 0.07			-14.34
313.15	6.47 ± 0.10			-13.97

图6 不同温度下SO2在三乙二醇二甲醚中的解吸率

Fig.6 Desorption rate of SO2 in triethylene glycol dimethyl ether at different temperature

图7 三乙二醇二甲醚 + SO2的紫外光谱图(变化趋势随SO2浓度增大)

Fig.7 UV-Vis spectra of triethylene glycol dimethyl ether + SO2 with the change trend of increased concentration of SO2

图8 三乙二醇二甲醚吸收SO2前后的红外光谱图

Fig.8 FTIR spectra of triethylene glycol dimethyl ether before and after SO2 absorption

图9 三乙二醇二甲醚吸收SO2前后的核磁氢谱(a)和碳谱(b)图

Fig.9 1H NMR (a) and 13C NMR (b) spectra of triethylene glycol dimethyl ether before and after SO2 absorption

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三乙二醇二甲醚吸收低浓度SO₂性能及机理研究

Study on performance and mechanism of triethylene glycol dimethyl ether for capturing low concentration SO₂

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