Phase diagram of pyridyl ionic liquid + organic salt aqueous two-phase system and study of salting-out ability

LIN Xuliang; XU Shuai; XU Shaojie; YUAN Manjing; CHEN Jinzhu; LI Yuliang; QIN Yanlin

doi:10.11949/0438-1157.20200243

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Phase diagram of pyridyl ionic liquid + organic salt aqueous two-phase system and study of salting-out ability

Thermodynamics | 更新时间：2026-07-24

- Phase diagram of pyridyl ionic liquid + organic salt aqueous two-phase system and study of salting-out ability
- CIESC Journal Vol. 71, Issue 11, Pages: 5067-5079(2020)
- 作者机构：
  
  1.广东工业大学轻工化工学院，广东广州 510006
  2.长安大学水利与环境学院，旱区地下水文与生态效应教育部重点实验室，陕西西安 710064
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200243
  CLC： TQ 028.8
- Received：10 March 2020，
  
  Revised：2020-08-01，
  
  Online First：03 November 2020，
  
  Published：05 November 2020
- 稿件说明：
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林绪亮, 徐帅, 徐少杰, 袁慢景, 陈金珠, 李宇亮, 秦延林. 吡啶基离子液体+有机盐双水相体系相图的测定及盐析性能研究[J]. 化工学报, 2020, 71(11): 5067-5079

LIN Xuliang, XU Shuai, XU Shaojie, YUAN Manjing, CHEN Jinzhu, LI Yuliang, QIN Yanlin. Phase diagram of pyridyl ionic liquid + organic salt aqueous two-phase system and study of salting-out ability[J]. CIESC Journal, 2020, 71(11): 5067-5079
林绪亮, 徐帅, 徐少杰, 袁慢景, 陈金珠, 李宇亮, 秦延林. 吡啶基离子液体+有机盐双水相体系相图的测定及盐析性能研究[J]. 化工学报, 2020, 71(11): 5067-5079 DOI： 10.11949/0438-1157.20200243.

LIN Xuliang, XU Shuai, XU Shaojie, YUAN Manjing, CHEN Jinzhu, LI Yuliang, QIN Yanlin. Phase diagram of pyridyl ionic liquid + organic salt aqueous two-phase system and study of salting-out ability[J]. CIESC Journal, 2020, 71(11): 5067-5079 DOI： 10.11949/0438-1157.20200243.

摘要

测定了离子液体

-乙基吡啶四氟硼酸盐([EPy

]

)+有机盐[丁二酸钠（CH

COONa)

/柠檬酸铵C

(NH

)

/柠檬酸钠C

]

+水双水相体系在303.15、308.15和313.15 K下的双节线及系线数据。基于相图中的杠杆定律通过质量法研究双水相体系的系线，并用Othmer-Tobias方程、Bancroft方程等经验方程以及NRTL活度系数模型对数据进行关联。采用有效排除体积和Setschenow-type的拟合参数深入研究三种有机盐的盐析能力。结果表明，双节线的三个经验式拟合效果良好，但较多参数的经验式会导致部分参数失去意义；双水相体系的系线满足经验方程，数据可靠性较好，且均方根偏差表明系线数据很好地符合NRTL模型；低温更有利于该双水相体系的形成；三种盐都能和[EPy

]

离子液体形成双水相体系，且C

的盐析能力更优。本文提供的数据为离子液体的回收循环利用提供了理论参考依据。

Abstract

The binodal curve and tie-line data of

-ethylpyridinium tetrafluoroborate ([EPy

]

) + organic salts [sodium succinate((CH

COONa)

)/ammonium citrate (C

(NH

)

)/sodium citrate(C

)

]

ionic liquid-based aqueous two-phase systems have been studied. The tie-line data were determined using gravimetric method based on the lever rule. Then

the Othmer-Tobias

Bancroft equations and NRTL model were used to fit the data. The effective excluded volume of salt and Setschenow-type equation were used to investigate the salting-out ability of the three salts. As a result

all the t

hree empirical equations fit the binodal curves well

but some redundant parameters may be meaningless. The tie-lines data were satisfactory correlated to the equations

and show that the data is reliable. The root-mean-square deviation (RMSD) indicates tie-lines data fit NRTL model very well. The two-phase systems are easier to form at lower temperatures. All the three salts can form aqueous two-phase system with [EPy

]

and C

possesses stronger salting-out ability. The data provided in this article provides a theoretical reference for the recycling of ionic liquids.

关键词

Keywords

references

Iqbal M , Tao Y , Xie S , et al . Aqueous two-phase system (ATPS): an overview and advances in its applications [J ] . Biological Procedures Online , 2016 , 18 ( 1 ): 18 .

周红航 , 王维香 . 聚乙二醇/硫酸铵双水相体系萃取猪胰蛋白酶 [J ] . 化工进展 , 2009 , 28 ( 2 ): 305 - 308 .

Zhou H H , Wang W X . Extraction of porcine trypsin from a polyethylene glycol/ammonium sulfate two-phase system [J ] . Chemical Industry and Engineering Progress , 2009 , 28 ( 2 ): 305 - 308 .

Dupont J , de Souza R F , Suarez P A Z . Ionic liquid (molten salt) phase organometallic catalysis [J ] . Chemical Reviews , 2002 , 102 ( 10 ): 3667 - 3692 .

Gutowski K E , Broker G A , Willauer H D , et al . Controlling the aqueous miscibility of ionic liquids: aqueous biphasic systems of water-miscible ionic liquids and water-structuring salts for recycle, metathesis, and separations [J ] . J. Am. Chem. Soc. , 2003 , 125 : 6632 - 6633 .

Freire M G , Claudio A F M , Araujo J M M , et al . Aqueous biphasic systems: a boost brought about by using ionic liquids [J ] . Chemical Society Reviews , 2012 , 41 ( 14 ): 4966 - 4995 .

徐晓冬 , 丹媛媛 , 李欣欣 , 等 . 离子液体双水相体系及其在生物分离中的应用 [J ] . 生物技术通报 , 2008 , ( 5 ): 88 - 91 .

Xu X D , Dan Y Y , Li X X , et al . Ionic liquid two-aqueous system and its application in biological separation [J ] . Biotechnology Bulletin , 2008 , ( 5 ): 88 - 91 .

刘丙艳 , 刘培元 , 王国平 , 等 . [Bmim ] BF 4 -H 2 O-Na 2 CO 3 离子液体双水相体系液液相平衡数据的测定与关联 [J ] . 化工学报 , 2007 , 58 ( 8 ): 1885 - 1890 .

Liu B Y , Liu P Y , Wang G P , et al . Measurement and correlation of liquid-liquid equilibrium data for ionic liquid-based aqueous two-phase system of [Bmim ] BF 4 -H 2 O-Na 2 CO 3 [J ] . Journal of Chemical Industry and Engineering (China) , 2007 , 58 ( 8 ): 1885 - 1890 .

赵晓军 , 田刚 , 李鑫垚 , 等 . [Bmim ] BF 4 /EA-(NH 4 ) 2 SO 4 -H 2 O双水相体系萃取黄连中盐酸小檗碱 [J ] . 山东化工 , 2017 , 46 ( 18 ): 14 - 17 .

Zhao X J , Tian G , Li X Y , et al . Extraction berberine hydrochloride from coptis by [Bmim ] BF 4 /EA-(NH 4 ) 2 SO 4 -H 2 O aqueous two-phase system [J ] . Shandong Chemical Industry , 2017 , 46 ( 18 ): 14 - 17 .

蔡涛 , 张海德 , 董安华 , 等 . 木瓜蛋白酶在[C n mim ] BF 4 -NaH 2 PO 4 双水相体系中的分配行为 [J ] . 化工学报 , 2015 , 66 ( 6 ): 2017 - 2022 .

Cai T , Zhang H D , Dong A H , et al . Partition behavior of papain in [C n mim ] BF 4 -NaH 2 PO 4 aqueous two-phase system [J ] . CIESC Journal , 2015 , 66 ( 6 ): 2017 - 2022 .

余垒 , 朱新儒 , 曾颖 , 等 . [N 2,2,2,2 ] BF 4 的合成及其对双水相体系成相行为的影响 [J ] . 无机盐工业 , 2019 , 51 ( 10 ): 22 - 27 .

Yu L , Zhu X R , Zeng Y , et al . Synthesis of [N 2,2,2,2 ] BF 4 and its effect on phase formation behavior of aqueous two-phase system [J ] . Inorganic Chemicals Industry , 2019 , 51 ( 10 ): 22 - 27 .

朱新儒 , 张海德 , 余垒 . Box-Behnken响应面法优化 [CnPy ] Cl (n=2 , 4 , 6)-K 2 HPO 4 双水相体系萃取木瓜蛋白酶 [J ] . 食品科技 , 2018 , 43 ( 9 ): 290 - 297 .

Zhu X R , Zhang H D , Yu L . Optimization of [CnPy ] Cl (n=2 , 4 , 6)-K 2 HPO 4 ionic liquid aqueous two-phase system extraction of papain using response surface methodology with Box-Behnken design [J ] . Food Science and Technology , 2018 , 43 ( 9 ): 290 - 297 .

Li Y , Lu X , He W , et al . Influence of the salting-out ability and temperature on the liquid–liquid equilibria of aqueous two-phase systems based on ionic liquid–organic salts–water [J ] . Journal of Chemical & Engineering Data , 2016 , 61 ( 1 ): 475 - 486 .

Oppermann S , Stein F , Kragl U . Ionic liquids for two-phase systems and their application for purification,extraction and biocatalysis [J ] . Applied microbiology and Biotechnology , 2011 , 89 ( 3 ): 493 - 499 .

Gómez E , Macedo E A . Partitioning of DNP-amino acids in ionic liquid/citrate salt based aqueous two-phase system [J ] . Fluid Phase Equilibria , 2019 , 484 : 82 - 87 .

邓凡政 , 郭东方 . 离子液体双水相体系萃取分离牛血清白蛋白 [J ] . 分析化学 , 2006 , 34 ( 10 ): 1451 - 1453 .

Deng F Z , Guo D F . Extraction and separation of bovine serum albumin in ionic liquid two-aqueous system [J ] . Chinese Journal of Analytical Chemistry , 2006 , 34 ( 10 ): 1451 - 1453 .

Guo J , Xu S , Qin Y , et al . The temperature influence on the phase behavior of ionic liquid based aqueous two-phase systems and its extraction efficiency of 2-chlorophenol [J ] . Fluid Phase Equilibria , 2020 , 506 : 112394 .

Petkovic M , Seddon K R , Rebelo L P N , et al . Ionic liquids: a pathway to environmental acceptability [J ] . Chemical Society Reviews , 2011 , 40 ( 3 ): 1383 - 1403 .

Garcia M T , Gathergood N , Scammells P J . Biodegradable ionic liquids <math id="M21"><mo stretchy="false">(</mo><mi mathvariant="normal">Ⅱ</mi><mo stretchy="false">)</mo></math> https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113892766&type= https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113892752&type= 3.55599999 2.79399991 : Effect of the anion and toxicology [J ] . Green Chemistry , 2005 , 7 ( 1 ): 9 - 14 .

Petkovic M , Seddon K R , Rebelo L P , et al . Ionic liquids: a pathway to environmental acceptability [J ] . Chemical Society Reviews , 2011 , 40 ( 3 ): 1383 - 1403 .

高鹏 . 不同碳链长度的离子液体对蛋白核小球藻的毒性影响研究 [J ] . 安徽化工 , 2017 , 43 ( 4 ): 44 - 46 .

Gao P . Toxicity effects of ionic liquids with different carbon chain length on Chlorella proteus [J ] . Anhui Chemical Industry , 2017 , 43 ( 4 ): 44 - 46 .

王全泽 , 袁堂丰 , 瞿利民 , 等 . 微胶囊双水相法提取罗汉松挥发油及成分分析 [J ] . 精细化工 , 2019 , 36 ( 4 ): 684 - 690 .

Wang Q Z , Yuan T F , Qu L M , et al . Extraction of volatile oil from podocarpus macrophyllus by microcapsule aqueous two-phase system and its composition analysis [J ] . Fine Chemicals , 2019 , 36 ( 4 ): 684 - 690 .

董彩文 , 王浩瑾 , 张明俊 , 等 . 双水相技术提取黄秋葵黄酮的工艺条件研究 [J ] . 粮食与油脂 , 2019 , 32 ( 10 ): 85 - 88 .

Ding C W , Wang H J , Zhang M J , et al . Study on extraction of flavonoids from okra by aqueous two-phase technology [J ] . Cereals & Oils , 2019 , 32 ( 10 ): 85 - 88 .

王丽 , 费春芳 . 两种双水相体系提取枇杷叶中黄酮的工艺研究 [J ] . 化学与生物工程 , 2014 , 31 ( 4 ): 55 - 59 .

Wang L , Fei C F . Study on extraction technology of elavonoids from loquat leaves by two kinds of aqueous two-phase systems [J ] . Chemistry & Bioengineering , 2014 , 31 ( 4 ): 55 - 59 .

李青云 , 袁凤梅 , 吴金英 . 聚乙二醇/硫酸钠双水相萃取赖氨酸 [J ] . 食品与发酵工业 , 2014 , 40 ( 4 ): 221 - 226 .

Li Q Y , Yuan F M , Wu J Y . Investigation on extraction of L-lysine by a polyethylene glycol /sodium sulfate aqueous two-phase system [J ] . Food and Fermentation Industries , 2014 , 40 ( 4 ): 221 - 226 .

Xu S , Zhu Q , Luo Q , et al . Influence of ions and temperature on aqueous biphasic systems containing ionic liquid and ammonium sulfate [J ] . Journal of Chemical & Engineering Data , 2019 , 64 ( 7 ): 3139 - 3147 .

李宇亮 , 杨思语 , 张文杉 . 温敏性离子液体氯化 N -丁基吡啶双水相体系相图的测定及关联 [J ] . 高校化学工程学报 , 2016 , 30 ( 6 ): 1445 - 1450 .

Li Y L , Yang S Y , Zhang W S . Determination and correlation of phase diagrams of thermosensitive ionic liquid chlorinated N -butylpyridine aqueous two phase system [J ] . Journal of Chemical Engineering of Chinese Universities , 2016 , 30 ( 6 ): 1445 - 1450 .

Merchuk J C , Andrews B A , Asenjo J A . Aqueous two-phase systems for protein separation: studies on phase inversion [J ] . Journal of Chromatography B: Biomedical Sciences and Applications , 1998 , 711 ( 1/2 ): 285 - 293 .

Guan Y , Lilley T H , Treffry T E . A new excluded volume theory and its application to the coexistence curves of aqueous polymer two-phase systems [J ] . Macromolecules , 1993 , 26 ( 15 ): 3971 - 3979 .

Hey M J , Jackson D P , Yan H . The salting-out effect and phase separation in aqueous solutions of electrolytes and poly (ethylene glycol) [J ] . Polymer , 2005 , 46 ( 8 ): 2567 - 2572 .

Li Y , Xu Z , Luo Q , et al . Phase diagram of ionic liquid aqueous two-phase systems with N -butylpyridinium tetrafluoroborate, ammonium Citrate/Sodium acetate, and water from 308.15 K to 328.15 K [J ] . Thermochimica Acta , 2016 , 632 : 72 - 78 .

Alvarez-Guerra E , Ventura S P M , Alvarez-Guerra M , et al . Modeling of the binodal curve of ionic liquid/salt aqueous systems [J ] . Fluid Phase Equilibria , 2016 , 426 : 10 - 16 .

Wang Y , Yan Y , Hu S , et al . Phase diagrams of ammonium sulfate+ethanol/1-propanol/2-propanol + water aqueous two-phase systems at 298.15 K and correlation [J ] . Journal of Chemical & Engineering Data , 2010 , 55 ( 2 ): 876 - 881 .

Othmer D F , Tobias P E . Liquid-liquid extraction data-toluene and acetaldehyde systems [J ] . Industrial & Engineering Chemistry , 1942 , 34 ( 6 ): 690 - 692 .

Bancroft W D , Hubard S S . A new method for determining dineric distribution [J ] . Journal of the American Chemical Society , 1942 , 64 ( 2 ): 347 - 353 .

Rodriguez-Escontrela I , Arce A , Soto A , et al . Correlation of three-liquid-phase equilibria involving ionic liquids [J ] . Physical Chemistry Chemical Physics , 2016 , 18 ( 31 ): 21610 - 21617 .

Marcus Y . Thermodynamics of solvation of ions(Part 5): Gibbs free energy of hydration at 298.15 K [J ] . Journal of the Chemical Society , Faraday Transactions , 1991 , 87 ( 18 ): 2995 - 2999 .

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