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

doi:10.11949/0438-1157.20200884

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 11

Fig.1 Sketch of the experimental apparatus

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

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

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

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

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

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

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

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

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

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

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

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

三乙二醇二甲醚吸收低浓度SO₂性能及机理研究

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