离子液体和醇胺溶液复配脱硫剂吸收H2S及再生性能

doi:10.7503/cjcu20140108

摘要/Abstract

摘要：

将5种离子液体[Bmim]HCO₃, [TMG]L, [MEA]L, [Bmim]Cl和[Bmim]BF₄分别与N-甲基二乙醇胺(MDEA)水溶液混合, 得到新型复配脱硫剂, 考察了离子液体的消泡性能和复配脱硫剂在不同离子液体、吸收温度以及复配比例下的脱硫性能, 并且对较优脱硫剂进行了再生性能的研究. 采用离子色谱仪对经臭氧深度处理的再生液进行了S $O 4 2 -$ 离子浓度测试, 并对脱硫剂进行了密度泛函理论研究, 从而进一步分析了吸收机理. 结果表明, 室温下复配脱硫剂脱硫能力大小顺序为[Bmim]Cl-MDEA-H₂O>[Bmim]HCO₃-MDEA-H₂O>[Bmim]BF₄-MDEA-H₂O>MDEA-H₂O>[TMG]L-MDEA-H₂O>[MEA]L-MDEA-H₂O. 离子液体与MDEA结合的稳定性为主要影响因素, [Bmim]HCO₃的消泡能力最强, [Bmim]Cl-MDEA-H₂O, [Bmim]BF₄-MDEA-H₂O和[Bmim]HCO₃-MDEA-H₂O脱硫剂可以通入空气获得基本再生, H₂S与离子液体的结合越稳定, 脱硫效率越高, 但脱硫剂的再生程度会降低.

关键词: 硫化氢, 离子液体, N-甲基二乙醇胺, 脱硫剂, 密度泛函理论

Abstract:

Three kinds of functionalized ionic liquids [Bmim]HCO₃, [TMG]L and [MEA]L were synthesized. The structure and thermostability of the synthetic ionic liquids(ILs) were confirmed by FTIR spectrum and thermogravimetry characterization, respectively. The new combined desulfurizers were prepared by mixing ionic liquid([Bmim]HCO₃, [TMG]L, [MEA]L, [Bmim]Cl or [Bmim]BF₄) with methyldiethanolamine(MDEA) aqueous solution according to certain proportion. Under conditions of different ionic liquids, absorption temperature and desulfurizer composition, H₂S absorption and bubble eliminating capacity of the desulfurizer were measured, and regeneration performance of the favorable desulfurizer was studied. The concentration of S $O 4 2 -$ in regenerated desulfurizer was analyzed by ion chromatography after deep oxidation by O₃, and the mechanism of absorption was analyzed based on the calculations from density functional theory. The results show that absorption capacity is in the sequence of [Bmim]Cl-MDEA-H₂O>[Bmim]HCO₃-MDEA-H₂O>[Bmim]BF₄-MDEA-H₂O>MDEA-H₂O>[TMG]L-MDEA-H₂O>[MEA]L-MDEA-H₂O, and the major factor is attributed to the stability of IL-MDEA; [Bmim]HCO₃ performs the best capacity of bubble elimination; [Bmim]Cl-MDEA-H₂O, [Bmim]HCO₃-MDEA-H₂O and [Bmim]BF₄-MDEA-H₂O can be nearly completely regenerated by air, and high stability of IL-H₂S leads to higher absorption efficiency, but smaller extent of regeneration.

Key words: H2S, Ionic liquid, Methyldiethanolamine(MDEA), Desulfurizer, Density functional theory

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马云倩, 王睿. 离子液体和醇胺溶液复配脱硫剂吸收H₂S及再生性能. 高等学校化学学报, 2014, 35(7): 1515.

MA Yunqian, WANG Rui. H₂S Absorption Capacity of Ionic Liquid-MDEA-H₂O Combined Desulfurizers^†. Chem. J. Chinese Universities, 2014, 35(7): 1515.

图/表 9

Fig.1 FTIR spectra of [Bmim]HCO3(A), [TMG]L(B) and [MEA]L(C)

Fig.2 TGA(a) and DSC(b) curves of [Bmim]HCO3(A), [TMG]L(B) and [MEA]L(C)

Fig.3 H2S absorption efficiency as a function of time on different IL-MDEA-H2O combined desulfurizers

Fig.4 H2S absorption efficiency by [Bmim]Cl-MDEA-H2O combined deoxidizer as a function of time at 28 ℃(a), 60 ℃(b) and 80 ℃(c) Desulfurizer: 10 mL; [Bmim]Cl: 1 g; MDEA: 3 g.

Table 1 H2S absorption capacity and sulfur capacity of [Bmim]Cl-MDEA-H2O combined eoxidizer with different component

m(MDEA)/g	m([Bmim]Cl)/g	H₂S removal efficiency^a(%)	Capacity of sulfur^c/(g·L^-1)	m(MDEA)/g	m([Bmim]Cl)/g	H₂S removal efficiency^a(%)	Capacity of sulfur^c/(g·L^-1)
0	0	17.6^b		3	0.5	93.0	3.36
0	10	9.8^b		3	1	94.4	3.66
0	1	14.9^b		3	1.5	95.0	3.74
1	0	72.5	1.56	3	2	96.2	3.95
1	0.5	84.0	2.21	5	0	89.1	3.01
1	1	86.8	2.53	5	0.5	93.9	3.42
1	1.5	87.6	2.64	5	1	94.8	3.68
1	2	88.7	2.75	5	1.5	96.3	4.01
3	0	84.8	2.42	5	2	97.4	4.31

Table 2 Capacity of ILs on eliminating bubbles

Desulfurizer	m(MDEA)/g	m(IL)/g	Bubbling height/cm	Efficiency(%)
MDEA-H₂O	0.5	0	22
MDEA-[Bmim]Cl-H₂O	0.5	0.5	16.9	23.2
MDEA-[Bmim]BF₄-H₂O	0.5	0.5	15.2	30.9
MDEA-[TMG]L-H₂O	0.5	0.5	22.1	0
MDEA-[MEA]L-H₂O	0.5	0.5	20.5	6.8
MDEA-[Bmim]HCO₃-H₂O	0.5	0.5	11.8	46.4
MDEA-[Bmim]HCO₃-H₂O	0.5	1.5	7.8	64.5

Fig.5 Chemical structures of [Bmim]Cl, [Bmim]BF4, [Bmim]HCO3, [TMG]L and [MEA]L

Table 3 Energetics data on IL-MDEA , IL-H2S and MDEA-H2S

Compd.	MDEA			H₂S
Compd.	$E 0 a$ /(kJ·mol^-1)	$E t b$ /(kJ·mol^-1)	ΔH^c/(kJ·mol^-1)	E_t/(kJ·mol^-1)	ΔH/(kJ·mol^-1)
1	-3702.3	-5393.4	-59.5	-5375.8	-32.3
2	-3552.7	-5243.8	-30.6	-5226.2	-18.9
3	-2881.9	-4573.0	-34.8	-4555.4	-32.7
4	-2959.4	-4650.5	-14.2	-4632.9	-28.1
5	-2651.0	-4342.1	-4.19	-4324.5	13.0
MDEA	-1691.1			-3364.6	-13.4
H₂O	-320.1			-1993.6	-14.7

Table 3 Energetics data on IL-MDEA , IL-H2S and MDEA-H2S

Compd.	MDEA			H₂S
Compd.	$E 0 a$ /(kJ·mol^-1)	$E t b$ /(kJ·mol^-1)	ΔH^c/(kJ·mol^-1)	E_t/(kJ·mol^-1)	ΔH/(kJ·mol^-1)
1	-3702.3	-5393.4	-59.5	-5375.8	-32.3
2	-3552.7	-5243.8	-30.6	-5226.2	-18.9
3	-2881.9	-4573.0	-34.8	-4555.4	-32.7
4	-2959.4	-4650.5	-14.2	-4632.9	-28.1
5	-2651.0	-4342.1	-4.19	-4324.5	13.0
MDEA	-1691.1			-3364.6	-13.4
H₂O	-320.1			-1993.6	-14.7

Table 4 Regeneration analysis data of desulfurizer

Desulfurizer	c(S $O 4 2 -$ ) ^a/(g·L^-1)	Residue sulfur^b/(g·L^-1)	Sulfur capacity/(g·L^-1)	Regeneration efficiency^c(%)
[Bmim]Cl-MDEA-H₂O	0.041	0.135	2.53	94.66
[Bmim]BF₄-MDEA-H₂O	0.027	0.090	1.76	94.89
[Bmim]HCO₃-MDEA-H₂O	0.036	0.120	2.28	94.74

Table 4 Regeneration analysis data of desulfurizer

Desulfurizer	c(S $O 4 2 -$ ) ^a/(g·L^-1)	Residue sulfur^b/(g·L^-1)	Sulfur capacity/(g·L^-1)	Regeneration efficiency^c(%)
[Bmim]Cl-MDEA-H₂O	0.041	0.135	2.53	94.66
[Bmim]BF₄-MDEA-H₂O	0.027	0.090	1.76	94.89
[Bmim]HCO₃-MDEA-H₂O	0.036	0.120	2.28	94.74

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离子液体和醇胺溶液复配脱硫剂吸收H₂S及再生性能

H₂S Absorption Capacity of Ionic Liquid-MDEA-H₂O Combined Desulfurizers^†

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