苯甲酸型低共熔溶剂吸收一氧化氮的性能研究

doi:10.11949/0438-1157.20200116

摘要/Abstract

摘要：

低共熔溶剂（DESs）已被广泛研究并应用于酸性气体的吸收，本研究发现苯甲酸类DESs能够可逆高效地吸收一氧化氮（NO）。以苯甲酸（BA）、硫脲、尿素和咪唑为氢键供体（HBD），以离子液体为氢键受体（HBA）制备了一系列的DESs。吸收NO的实验结果表明，以氯化四丁基膦（P₄₄₄₄Cl）为HBA和以BA为HBD的DESs表现出较高的NO吸收速率和饱和吸收量。BA/P₄₄₄₄Cl (1∶2) DES在101.3 kPa、303.15 K下，NO吸收量为2.75 mol/mol。热重测试和再生实验的结果表明，BA/P₄₄₄₄Cl (1∶2) DES具有理想的热稳定性和重复使用性。通过FTIR、¹H NMR和高斯模拟计算，探讨了BA/P₄₄₄₄Cl (1∶2) DES对NO的吸收机理，发现NO与BA的含氢氧原子之间存在化学相互作用，且BA的易去质子化性质有利于NO的吸收。

关键词: 低共熔溶剂, 吸收, 一氧化氮, 苯甲酸, 氢键供体, 氢键受体

Abstract:

Deep eutectic solvents (DESs) have been extensively studied and applied to the absorption of acid gases. This study found that benzoic acid DESs can reversibly and efficiently absorb nitric oxide (NO). A series of DESs based on benzoic acid (BA), thiourea, urea, imidazole as hydrogen bond donors (HBDs) and ionic liquids as hydrogen bond acceptors (HBAs) were prepared. The NO absorption results showed that DESs based by tetrabutylphosphine chloride (P₄₄₄₄Cl) as HBA and BA as HBD exhibited the higher NO absorption rate and NO equilibrium absorption. BA/P₄₄₄₄Cl (1∶2) DES exhibited the NO absorption of 2.75 mol/mol at 101.3 kPa and 303.15 K. The NO absorption capacity decreased continuously with the increasing temperature. The results of TGA measurement and regeneration experiments demonstrated that BA/P₄₄₄₄Cl (1∶2) DES possessed desirable thermostability and reusability. The absorption mechanism of NO by BA/P₄₄₄₄Cl (1∶2) DES was studied by FTIR, ¹H NMR and Gaussian simulations. It was found that there was chemical interaction between NO and hydrogen-containing oxygen atom of BA, and the easily deprotonated nature of BA facilitates the absorption of NO.

Key words: DES, absorption, nitric oxide, benzoic acid, HBD, HBA

中图分类号:

X 511

张吕鸿, 马号朋, 澹台晓伟, 杨娜. 苯甲酸型低共熔溶剂吸收一氧化氮的性能研究[J]. 化工学报, 2020, 71(8): 3644-3651.

Lyuhong ZHANG, Haopeng MA, Xiaowei TANTAI, Na YANG. Study on the absorption of nitric oxide by benzoic acid-based deep eutectic solvents[J]. CIESC Journal, 2020, 71(8): 3644-3651.

图/表 13

图1 NO吸收实验装置流程示意图1—N2气瓶；2—NO气瓶；3—减压阀；4—气体流量计；5—气体混合器；6—质量流量计；7，10—三通阀；8—吸收瓶；9—数字恒温水浴；11—尾气吸收瓶

Fig.1 Schematic diagram of the NO absorption experiment

图2 不同HBD的DESs对NO吸收性能的影响

Fig.2 Effect of DESs of different HBD on NO absorption performance

图3 不同HBA的DESs对NO吸收性能的影响

Fig.3 Effect of DESs of different HBA on NO absorption performance

图4 不同摩尔比的DESs对NO吸收性能的影响

Fig.4 Effect of DESs with different molar ratios on NO absorption performance

图5 温度对DES吸收NO的影响

Fig.5 Effect of temperature on NO absorption by DES

图6 BA和BA/P4444Cl（1∶2）DES的热重曲线

Fig.6 Thermogravimetric curves of BA and BA/P4444Cl (1∶2) DES

图7 BA/P4444Cl（1∶2）DES的重复使用性

Fig.7 Repeatability of BA/P4444Cl (1∶2) DES

图8 BA/P4444Cl（1∶2）DES 吸收NO前后的FTIR光谱

Fig.8 FTIR spectra of BA/P4444Cl (1∶2) DES before and after absorption of NO

图9 BA和DES吸收NO前后1H NMR光谱

Fig.9 1H NMR spectra before and after absorption of NO by BA and DES

图10 BA/P4444Cl（1∶2）DES吸收NO的机理

Fig.10 Mechanism of NO absorption by BA/P4444Cl (1∶2) DES

图11 四种HBDs的核心原子的mulliken原子电荷

Fig.11 Mulliken atomic charge of the core atoms of four HBDs

图12 Cl-和Br-对BA的去质子化程度

Fig.12 Degree of deprotonation of BA by Cl- and Br-

表1 不同DESs和ILs的NO吸收量

Table 1 NO absorption of different DESs and ILs

吸收剂（摩尔比）	吸收温度 (解吸条件)/K	NO吸收量/		文献
吸收剂（摩尔比）	吸收温度 (解吸条件)/K	(mol/mol)	(g/g)	文献
BA/P₄₄₄₄Cl (1∶2)	303.15/(363.15)	2.75	0.116	本文
BA/P₄₄₄₄Br (1∶2)	303.15	1.79	0.067	本文
BA/BmimCl (1∶2)	303.15	1.32	0.084	本文
BA/BmimCl (1∶1)	303.15	0.79	0.080	本文
BA/BmimCl (2∶1)	303.15	1.62	0.115	本文
BA/BmimCl (3∶1)	303.15	2.70	0.149	本文
BA/BmimBr (1∶2)	303.15	0.95	0.051	本文
Thu/BmimCl (1∶1)	303.15	0.65	0.078	本文
Urea/BmimCl (1∶1)	303.15	0.57	0.073	本文
Imid/BmimCl (1∶1)	303.15	0.28	0.035	本文
Tetz/P₄₄₄₄Cl (1∶1)	303.15/(353.15)	2.10	0.173	[28]
Tetz/N₄₄₄₄Cl (1∶1)	303.15	1.46	0.126	[28]
Triz/P₄₄₄₄Cl (1∶1)	303.15	0.71	0.059	[28]
Tetz/ChCl	343.15	0.86	0.123	[28]
Imid/P₄₄₄₄Cl (1∶1)	303.15	0.16	0.013	[28]
[P₆₆₆₁₄][Tetz]	303.15/(353.15)	4.52	0.246	[15]
1,3-DMTU/P₄₄₄₄Cl (3∶1)	303.15/(353.15)	4.25	0.210	[23]
1,3-DMTU/P₄₄₄₄Cl (1∶1)	303.15	2.13	0.160	[23]
1,3-DMTU/N₄₄₄₄Cl (1∶1)	303.15	2.05	0.161	[23]
1,3-DMTU/P₄₄₄₄Br (1∶1)	303.15	1.13	0.076	[23]
1,3-DMU/P₄₄₄₄Br (1∶1)	303.15/(353.15)	0.66	0.046	[29]
CPL/N₄₄₄₄F (2∶1)	338.15(真空)	0.16	0.010	[21]

参考文献 29

1	Zhang X W, Tong H L, Zhang H, et al. Nitrogen oxides absorption on calcium hydroxide at low temperature [J]. Industrial & Engineering Chemistry Research, 2008, 47(11): 3827-3833.
2	Lei Z G, Liu X Y, Jia M R. Modeling of selective catalytic reduction (SCR) for NO removal using monolithic honeycomb catalyst [J]. Energy & Fuels, 2009, 23(12): 6146-6151.
3	Takeuchi M, Matsumoto S. NO_x storage-reduction catalysts for gasoline engines [J]. Topics in Catalysis, 2004, 28(1/2/3/4): 151-156.
4	Lim T H, Jeong S M, Kim S D, et al. Photocatalytic decomposition of NO by TiO₂ particles [J]. Journal of Photochemistry and Photobiology A-Chemistry, 2000, 134(3): 209-217.
5	Liu N, Lu B H, Zhang S H, et al. Evaluation of nitric oxide removal from simulated flue gas by Fe (Ⅱ) EDTA/Fe (Ⅱ) citrate mixed absorbents [J]. Energy & Fuels, 2012, 26(8): 4910-4916.
6	Bin L J, Done K S. Kinetics of NO_x reduction by urea solution in pilot scale reactor [J]. Journal of Chemical Engineering of Japan, 1996, 29(4): 620-626.
7	Sada E, Kumazawa H, Kudo I, et al. Absorption of lean NO_x in aqueous solutions of NaClO₂ and NaOH [J]. Industrial & Engineering Chemistry Process Design & Development, 1979, 18(2): 275-278.
8	Culotta E, Koshland D E. NO news is good news [J]. Science, 1992, 258(5090): 1862-1865.
9	Rogers D R. Chemistry: ionic liquids—solvents of the future? [J]. Science, 2003, 302(5646): 792-793.
10	Reetz M T, Wiesenhofer W, Francio G, et al. Continuous flow enzymatic kinetic resolution and enantiomer separation using ionic liquid/supercritical carbon dioxide media [J]. Advanced Synthesis & Catalysis, 2003, 345(11): 1221-1228.
11	Maton C, de Vos N, Stevens C V. Ionic liquid thermal stabilities: decomposition mechanisms and analysis tools [J]. Chemical Society Reviews, 2013, 42(13): 5963-5977.
12	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(18): 2415-2417.
13	Gonzalez-Miquel M, Bedia J, Abrusci C, et al. Anion effects on kinetics and thermodynamics of CO₂ absorption in ionic liquids [J]. Journal of Physical Chemistry B, 2013, 117(12): 3398-3406.
14	Wang X, Zeng S J, Wang J L, et al. Selective separation of hydrogen sulfide with pyridinium-based ionic liquids [J]. Industrial & Engineering Chemistry Research, 2018, 57(4): 1284-1292.
15	Chen K H, Shi G L, Zhou X Y, et al. Highly efficient nitric oxide capture by azole-based ionic liquids through multiple-site absorption [J]. Angewandte Chemie-International Edition, 2016, 55(46): 14362-14366.
16	Sun Y, Ren S H, Hou Y C, et al. Absorption of nitric oxide in simulated flue gas by a metallic functional ionic liquid [J]. Fuel Processing Technology, 2018, 178: 7-12.
17	Zhang Q H, Vigier K D O, Royer S, et al. Deep eutectic solvents: syntheses, properties and applications [J]. Chemical Society Reviews, 2012, 41(21): 7108-7146.
18	Yang D Z, Han Y L, Qi H B, et al. Efficient absorption of SO₂ by EmimCI-EG deep eutectic solvents [J]. ACS Sustainable Chemistry & Engineering, 2017, 5(8): 6382-6386.
19	Zubeir L F, Held C, Sadowski G, et al. PC-SAFT modeling of CO₂ solubilities in deep eutectic solvents [J]. Journal of Physical Chemistry B, 2016, 120(9): 2300-2310.
20	Deng D S, Gao B, Zhang C, et al. Investigation of protic NH₄SCN-based deep eutectic solvents as highly efficient and reversible NH₃ absorbents [J]. Chemical Engineering Journal, 2019, 358: 936-943.
21	Duan E H, Guo B, Zhang D D, et al. Absorption of NO and NO₂ in caprolactam tetrabutyl ammonium halide ionic liquids [J]. Journal of the Air & Waste Management Association, 2011, 61(12): 1393-1397.
22	Dou J X, Zhao Y Q, Yin F K, et al. Mechanistic study of selective absorption of NO in flue gas using EG-TBAB deep eutectic solvents [J]. Environmental Science & Technology, 2019, 53(2): 1031-1038.
23	Sun Y L, Wei G S, Tantai X W, et al. Highly efficient nitric oxide absorption by environmentally friendly deep eutectic solvents based on 1,3-dimethylthiourea [J]. Energy & Fuels, 2017, 31(11): 12439-12445.
24	Drago R S, Paulik F E. The reaction of nitrogen (Ⅱ) oxide with diethylamine [J]. Journal of the American Chemical Society, 1960, 82(1): 1819-1822.
25	Drago R S, Ragsdale R O, Eyman D P. A mechanism for the reaction of diethylamine with nitric oxide [J]. Journal of the American Chemical Society, 1961, 83(21): 4337-4339.
26	Hrabie J A, Keefer L K. Chemistry of the nitric oxide-releasing diazeniumdiolate (“nitrosohydroxylamine”) functional group and its oxygen-substituted derivatives [J]. Chemical Reviews, 2002, 102(4): 1135-1154.
27	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.
28	Zhang L H, Ma H P, Wei G S, et al. Efficient and reversible nitric oxide absorption by low-viscosity, azole-derived deep eutectic solvents [J]. Journal of Chemical and Engineering Data, 2019, 64(7): 3068-3077.
29	Jiang B, Lin W R, Zhang L H, et al. 1,3-Dimethylurea tetrabutylphosphonium bromide ionic liquids for NO efficient and reversible capture [J]. Energy & Fuels, 2016, 30(1): 735-739.

[1]	黄琮琪, 吴一梅, 陈建业, 邵双全. 碱性电解水制氢装置热管理系统仿真研究[J]. 化工学报, 2023, 74(S1): 320-328.
[2]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[3]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[4]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[5]	张瑞航, 曹潘, 杨锋, 李昆, 肖朋, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8纳米流体天然气乙烷回收工艺的产品纯度关键影响因素分析[J]. 化工学报, 2023, 74(8): 3386-3393.
[6]	胡兴枝, 张皓焱, 庄境坤, 范雨晴, 张开银, 向军. 嵌有超小CeO₂纳米粒子的碳纳米纤维的制备及其吸波性能[J]. 化工学报, 2023, 74(8): 3584-3596.
[7]	陈宇豪, 陈晓平, 马吉亮, 梁财. 市政污泥回转窑焚烧气态污染物排放特性研究[J]. 化工学报, 2023, 74(5): 2170-2178.
[8]	李木金, 胡松, 施德磐, 赵鹏, 高瑞, 李进龙. 环氧丁烷尾气溶剂吸收及精制工艺[J]. 化工学报, 2023, 74(4): 1607-1618.
[9]	杨灿, 孙雪琦, 尚明华, 张建, 张香平, 曾少娟. 相变离子液体体系吸收分离CO₂的研究现状及展望[J]. 化工学报, 2023, 74(4): 1419-1432.
[10]	何万媛, 陈一宇, 朱春英, 付涛涛, 高习群, 马友光. 阵列凸起微通道内气液两相传质特性研究[J]. 化工学报, 2023, 74(2): 690-697.
[11]	王煦清, 严圣林, 朱礼涛, 张希宝, 罗正鸿. 填料塔中有机胺吸收CO₂气液传质的研究进展[J]. 化工学报, 2023, 74(1): 237-256.
[12]	王永倩, 王平, 程康, 毛晨林, 刘文锋, 尹智成, Ferrante Antonio. 氨气/甲烷贫预混旋转湍流火焰稳定性及NO生成[J]. 化工学报, 2022, 73(9): 4087-4094.
[13]	刘潜, 张香兰, 李志平, 李玉龙, 韩梦醒. 油酚分离过程低共熔溶剂的筛选及萃取性能研究[J]. 化工学报, 2022, 73(9): 3915-3928.
[14]	姜焱龙, 张妮, 李淡然, 朱冰冰, 蒋怡晨, 陈海军, 朱跃钊. 基于COSMO-RS方法筛选离子液体用于焦油脱除[J]. 化工学报, 2022, 73(4): 1704-1713.
[15]	张逸伟, 唐海荣, 何勇, 朱燕群, 王智化. 臭氧低温氧化烟气脱硝过程中的氮平衡试验研究[J]. 化工学报, 2022, 73(4): 1732-1742.