N-杂环离子液体液固相变吸收SO2

doi:10.16085/j.issn.1000-6613.2019-0541

摘要/Abstract

摘要：

采用不同N含量及碱性的六元N-杂环三级胺与不同酸性的有机羧酸直接中和制备了一系列离子液体，并将其用于SO₂的捕集，发现制得的部分离子液体可液固相变吸收SO₂。通过探究不同N-杂环离子液体对SO₂的吸收负载量，发现离子液体的SO₂吸收性能受阳离子N含量以及阴、阳离子的pK_a共同影响。采用XRD、FTIR、元素分析、单晶衍射等表征手段对1,3,5-三甲基六氢-1,3,5-三嗪乙酸盐离子液体相变吸收SO₂的产物进行分析，单晶解析发现固体吸收产物为甲胺基甲磺酸，并进一步推测了该离子液体吸收SO₂的反应过程与相变机理，反应过程先是1,3,5-三甲基六氢-1,3,5-三嗪在酸性条件下分解成亚甲基甲胺，然后由于SO₂的亲核作用，导致亚甲基甲胺碳氮双键的断裂和产物碳硫单键的形成。

关键词: 离子液体, 二氧化硫, 相变, 吸收, 甲胺基甲磺酸

Abstract:

A serial of ionic liquids were prepared by direct neutralization of six-membered N-heterocyclic tertiary amine with different nitrogen contents and alkaline using organic carboxylic acids with different acidities. The ionic liquids were then used for SO₂ capture and some of them showed the phase change absorption behavior. By exploring the SO₂ absorption capacity using different N-heterocyclic ionic liquids, we found that the SO₂ absorption is affected by the cationic nitrogen content of ionic liquids as well as the pK_a value of the anions and cations. Using XRD, FTIR, elemental analysis and single crystal diffraction, we analyzed the phase change products of SO₂ absorption by 1,3,5-trimethylhexahydro-1,3,5-triazine acetate ionic liquid, and the solid absorption product was found to be methylaminomethanesulfonic acid. It is further speculated that 1,3,5-trimethylhexahydro-1,3,5-triazine is first decomposed into methylene methylamine under acidic conditions, and then, due to the nucleophilic attack of SO₂, the carbon-nitrogen double bond in methylene methylamine is broken with the formation of the carbon-sulfur single bond.

Key words: ionic liquids, sulfur dioxide, phase change, absorption, methylaminomethanesulfonic acid

中图分类号:

X701.3

谢旭豪,陈玲,许胜超,赵文波. N-杂环离子液体液固相变吸收SO₂[J]. 化工进展, 2019, 38(12): 5603-5611.

Xuhao XIE,Ling CHEN,Shengchao XU,Wenbo ZHAO. Liquid-solid phase change absorption of SO₂ by N-heterocyclic ionic liquid[J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5603-5611.

图/表 15

参考文献 53

1	SRIVASTAVA R K, JOZEWICZ W. Flue gas desulfurization: the state of the art[J]. Journal of the Air & Waste Management Association, 2011, 51(12): 1676-1688.
2	ORTIZ F J G, VIDAL F, OLLERO P, et al. Pilot-plant technical assessment of wet flue gas desulfurization using limestone[J]. Industrial & Engineering Chemistry Research, 2013, 45(4): 1466-1477.
3	RODRÍGUEZ-SEVILLA J, ÁLVAREZ M, DÍAZ M C, et al. Absorption equilibria of dilute SO₂ in seawater[J]. Journal of Chemical & Engineering Data, 2004, 49(6): 1710-1716.
4	XIANG G, DING H, ZHEN D, et al. Gas-liquid absorption reaction between (NH₄)₂SO₃ solution and SO₂ for ammonia-based wet flue gas desulfurization[J]. Applied Energy, 2010, 87(8): 2647-2651.
5	BRENNECKE J F, MAGINN E J. Ionic liquids: innovative fluids for chemical processing[J]. AIChE Journal, 2010, 47(11): 2384-2389.
6	BLANCHARD L A, DAN H, BECKMAN E J, et al. Green processing using ionic liquids and CO₂[J]. Nature, 1999, 399(6731): 28-29.
7	WELTON T. Room-temperature ionic liquids solvents for synthesis and catalysis[J]. Cheminform, 2011, 111(5): 2071-2084.
8	ARMAND M, ENDRES F, MACFARLANE D R, et al. Ionic-liquid materials for the electrochemical challenges of the future[J]. Nature Materials, 2009, 8(8): 621.
9	KARADAS F, ATILHAN M, APARICIO S. Review on the use of ionic liquids (ILs) as alternative fluids for CO₂ capture and natural gas sweetening[J]. Energy & Fuels, 2010, 24(11): 5817-5828.
10	WU W Z, HAN B X, GAO H X, et al. Desulfurization of flue gas: SO₂ absorption by an ionic liquid[J]. Angewandte Chemie, 2004, 43(18): 2415-2417.
11	ZHANG X, ZHANG X, DONG H, et al. Carbon capture with ionic liquids: overview and progress[J]. Energy & Environmentalence, 2012, 5(5): 6668-6681.
12	SCOVAZZO P, KIEFT J, FINAN D A, et al. Gas separations using non-hexafluorophosphate [PF₆]-anion supported ionic liquid membranes[J]. Journal of Membrane Science, 2004, 238(1): 57-63.
13	NOBLE R D, GIN D L. Perspective on ionic liquids and ionic liquid membranes[J]. Journal of Membrane Science, 2011, 369(1): 1-4.
14	HUDDLESTON J G，WILLAUER H D, SWATLOSKI R P, et al. Room temperature ionic liquids as novel media for ‘clean’ liquid-liquid extraction[J]. Chem. Commun., 1998(16): 1765-1766.
15	HUANG K, CHEN Y L, ZHANG X M, et al. SO₂ absorption in acid salt ionic liquids/sulfolane binary mixtures: experimental study and thermodynamic analysis[J]. Chemical Engineering Journal, 2014, 237(1): 478-486.
16	HONG S Y, IM J, PALGUNADI J, et al. Ether-functionalized ionic liquids as highly efficient SO₂ absorbents[J]. Energy & Environmental Science, 2011, 4(5): 1802-1806.
17	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(37): 16264-16269.
18	CUI G K, ZHAO N, LI Y N, et al. Limited number of active sites strategy for improving SO₂ capture by ionic liquids with fluorinated acetylacetonate anion[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(9): 7985-7992.
19	MENG X C, WANG J Y, XIE P T, et al. Structure and SO₂ absorption properties of guanidinium-based dicarboxylic acid ionic liquids[J]. Energy & Fuels, 2018, 32(2): 1956-1962.
20	ZHAO T X, LI Y F, ZHANG Y T, et al. Efficient SO₂ capture and fixation to cyclic sulfites by dual ether-functionalized protic ionic liquids without any additives[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(8): 10886-10895.
21	ZHAI L, QIN Z, HE C, et al. Hydroxyl ammonium ionic liquids synthesized by water-bath microwave: synthesis and desulfurization[J]. Journal of Hazardous Materials, 2010, 177(1): 807-813.
22	JIAN W, ZENG S, LU B, et al. Novel ether-functionalized pyridinium chloride ionic liquids for efficient SO₂ capture[J]. Industrial & Engineering Chemistry Research, 2014, 53(43): 16832-16839.
23	ZENG S, GAO H, ZHANG X, et al. Efficient and reversible capture of SO₂ by pyridinium-based ionic liquids[J]. Chemical Engineering Journal, 2014, 251(1): 248-256.
24	TAYLOR S F R, MCCLUNG M, MCREYNOLDS C, et al. Understanding the competitive gas absorption of CO₂ and SO₂ in superbase ionic liquids[J]. Industrial & Engineering Chemistry Research, 2018, 57(50): 17033-17042.
25	CUI G K, LI Y N, LIU J X, et al. Tuning environmentally friendly chelate-based ionic liquids for highly efficient and reversible SO₂ chemisorption[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 15292-15300.
26	LI W, LIU Y, WANG L H, et al. Using ionic liquid mixtures to improve the SO₂ absorption performance in flue gas[J]. Energy & Fuels, 2017, 31(2): 1771-1777.
27	HASIB-UR-RAHMAN M, SIAJ M, LARACHI F. CO₂ capture in alkanolamine/room-temperature ionic liquid emulsions: a viable approach with carbamate crystallization and curbed corrosion behavior[J]. International Journal of Greenhouse Gas Control, 2012, 6(3): 246-252.
28	EISINGER R S, KELLER G E. Process for CO₂ capture using ionic liquid that exhibits phase change[J]. Energy & Fuels, 2014, 28(11): 7070-7078.
29	SEO S, SIMONI L D, MA M T, et al. Phase-change ionic liquids for postcombustion CO₂ capture[J]. Energy & Fuels, 2015, 28(9): 5968-5977.
30	WANG Y, ZHAO W, CHAI M, et al. Phase-change absorption of SO₂ by imidazole in organic solvents and conversion of the absorption product in the presence of water and oxygen[J]. Energy & Fuels, 2017, 31(12): 13999-14006.
31	ZHAO Q, ZHAO W, CHAI M, et al. Phase-change absorption of SO₂ by N,N,N′,N′-tetramethyl-p-phenylenediamine in organic solvents and utilization of absorption product[J]. Energy & Fuels, 2018, 32(2): 2073-2080.
32	LI G M, ZHAO W B, CHAI M Y, et al. Liquid-liquid phase-change absorption of SO₂ using N,N-dimethylcyclohexylamine as absorbent and liquid paraffin as solvent[J]. Journal of Hazardous Materials, 2018, 360: 89-96.
33	CHAI M, ZHAO W, LI G, et al. Novel SO₂ phase-change absorbent: mixture of N,N-dimethylaniline and liquid paraffin[J]. Industrial & Engineering Chemistry Research, 2018, 57(37): 12502-12510.
34	XIAO L Y, SUO J Z, XING M L. Hydroxyl ammonium ionic liquids: synthesis, properties, and solubility of SO₂[J]. Journal of Chemical & Engineering Data, 2007, 2(52): 596-599.
35	刑其毅. 基础有机化学[M]. 3版. 北京: 高等教育出版社, 2005.
	XING Q Y. Basic organic chemistry[M]. 3rd ed. Beijing: Higher Education Press, 2005.
36	MENG X C, WANG J Y, JIANG H C, et al. Guanidinium-based dicarboxylic acid ionic liquids for SO₂ capture[J]. Journal of Chemical Technology & Biotechnology, 2017, 92(4): 767-774.
37	SHANG Y, LI H P, ZHANG S J, et al. Guanidinium-based ionic liquids for sulfur dioxide sorption[J]. Chemical Engineering Journal, 2011, 175: 324-329.
38	REN S, HOU Y, TIAN S, et al. What are functional ionic liquids for the absorption of acidic gases?[J]. Journal of Physical Chemistry B, 2013, 117(8): 2482-2486.
39	李绛, 谢代前, 鄢国森. 呋喃与HCl和CHCl₃构成的分子间氢键的理论研究[J]. 中国科学, 2003, 33(1): 21-25.
	LI J, XIE D Q, YAN G S. Theoretical study on intermolecular hydrogen bonds between furan and HCl and CHCl₃[J]. Science in China, 2003, 33(1): 21-25.
40	HOBZA P, HAVLAS Z. Blue-shifting hydrogen bonds[J]. Chemical Reviews, 2000, 100(11): 4253-4264.
41	ZHAO W, ZHAO Q, ZHANG Z, et al. Liquid-solid phase-change absorption of acidic gas by polyamine in nonaqueous organic solvent[J]. Fuel, 2017, 209: 69-75.
42	GIVAN A, LOEWENSCHUSS A, NIELSEN C J. Infrared spectrum and ab initio calculations of matrix isolated methanesulfonic acid species and its 1∶1 water complex[J]. Journal of Molecular Structure, 2005, 748(1): 77-90.
43	HUANG L, SONG T, YONG F, et al. Synthesis and characterization of a new chiral open-framework indium phosphite with intertwined host and guest helices[J]. Microporous & Mesoporous Materials, 2012, 149(1): 95-100.
44	GOWENLOCK B G, THOMAS K E. The gaseous equilibrium of 1,3,5-trimethylhexahydro-1,3,5-triazine and N-methylenernethylamhe[J]. Journal of the Chemical Society B: Physical Organic, 1966, 409/410.DOI:10.1039/J29ll0000409. DOI
45	FRANKEL M, MOSES P. Syntheses of amino alkyl sulphonic acids and their peptide analogues[J]. Tetrahedron, 1960, 9(3/4): 289–294.
46	大连理工大学无机化学教研室. 无机化学[M]. 5版. 北京: 高等教育出版社, 2006: 494.
	Department of Inorganic Chemistry, Dalian University of Technology. Inorganic chemistry[M]. 5nd ed. Beijing: Higher Education Press, 2006: 494.
47	GRYAZNOV P I, KATAEVA O N, NAUMOVA O E, et al. Reaction of β-iminoalcohols with sulfur dioxide. Synthesis of (±) -(2-hydroxyalkylamino) phenyl (isopropyl)-methanesulfonic acids[J]. Russian Journal of General Chemistry, 2010, 80(4): 761-764.
48	GRYGORENKO O O, BIITSEVA A V, ZHERSH S. Amino sulfonic acids, peptidosulfonamides and other related compounds[J]. Tetrahedron, 2018, 74(13): 1355-1421.
49	HELDEBRANT D J, KOECH P K, YONKER C R. A reversible zwitterionic SO₂-binding organic liquid[J]. Energy Environ. Sci., 2010, 3(1): 111-113.
50	YANG D, HOU M, NING H, et al. Efficient SO₂ capture by amine functionalized PEG[J]. Physical Chemistry Chemical Physics, 2013, 15(41): 18123-18127.
51	LONG R D, HILLIARD N P, CHHATRE S A, et al. Comparison of zwitterionic N-alkylaminomethanesulfonic acids to related compounds in the good buffer series[J]. Beilstein Journal of Organic Chemistry, 2010, 6(31): 1-7.
52	KHOMA R E, SHESTAKA A A, SHISHKIN O V, et al. Features of interaction in the sulfur(IV) oxide-hexamethylenetetramine-water system: a first example of identification of the product with a sulfur-carbon bond[J]. Russian Journal of General Chemistry, 2011, 81(3): 620-621.
53	KHOMA R E, GEL’MBOL’DT V O, ENNAN A A, et al. Synthesis, crystal structure, and spectral characteristics of N-(tert-butyl)aminomethanesulfonic acid[J]. Russian Journal of General Chemistry, 2015, 85(10): 2282-2284.

有机胺	pK_a
1-甲基哌啶	9.59
1,4-二甲基哌嗪	7.99
1,3,5-三嗪	6.5

有机胺	pK_a
1-甲基哌啶	9.59
1,4-二甲基哌嗪	7.99
1,3,5-三嗪	6.5

有机酸	pK_a
乙酸	4.79
甲酸	3.74
二氯乙酸	1.37
三氟乙酸	0.05

有机酸	pK_a
乙酸	4.79
甲酸	3.74
二氯乙酸	1.37
三氟乙酸	0.05

吸收体系	结果	C/%	H/%	N/%	S/%
[tmtz][Ac]+3SO₂	实验值1	20.1	6.61	11.26	26.25
	实验值2	20.02	6.19	10.98	25.91
[tmtz][Ac]+H₂O+3SO₂	实验值1	19.91	6.38	11.18	24.85
	实验值2	20	6.99	11.48	23.31
[tmtz][Ac]+3SO₂	理论值	22.41	4.66	13.07	29.88
[tmtz][Ac]+H₂O+3SO₂	理论值	21.22	5.00	12.38	28.29
[tmtz][Ac]+2H₂O+3SO₂	理论值	20.15	5.32	11.75	26.86
[tmtz][Ac]+3H₂O+3SO₂	理论值	19.18	5.59	11.19	25.58

N-杂环离子液体液固相变吸收SO₂

Liquid-solid phase change absorption of SO₂ by N-heterocyclic ionic liquid

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参考文献 53

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参数	C₂H₇NO₃S
分子质量	125.15
测试温度	(100±2)K
辐射波长	0.71073nm
晶系	正交
空间群	P2₁2₁2₁
晶胞参数	a=(5.3814±0.0007)?
	b=(7.7464±0.0009)?
	c=(11.8913±0.0015)?
晶胞体积	(495.71±0.11)?³
Z值	4
晶体密度	1.677mg/m³
吸收系数	0.546mm^-1
单胞中电子数目F(000)	264
晶体尺寸	0.570×0.130×0.100mm³
扫描范围	3.139°～30.673°
极限指数	-7≤h≤7 -10≤k≤10 -14≤l≤16
衍射点数目	5323
独立衍射点数目	1434 [R(int)=0.0204]
至25.242°的扫描完整度	99.5%
吸收校正方法	半经验
精修方法	基于F²的全矩阵最小二乘法
精修衍射点/限制数据/参数	1434/0/65
拟合优度	1.098
最终偏离因子[＞2(I)]	R1=0.0199, wR2=0.0519
偏离因子（全部数据）	R1=0.0211, wR2=0.0527
绝对结构参数	0.36±0.03
消光系数	n/a
最高峰与最低峰	0.358e·?与-0.229e·?

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