Mechanism of the Interaction Between Ionic Liquid [Bmim][DBP] and Methanol for Seperation of Mixed C4/Methanol†

doi:10.7503/cjcu20170629

Abstract

Abstract:

In this work, the extractive methanol removal from C₄ hydrocarbon using ionic liquids(ILs) as extractants was studied. Firstly, the effect of structure of ionic liquid on extraction process was investigated. The results show that 1-butyl-3-methyl imidazole dibutyl phosphate([Bmim][DBP]) performs the best extraction. According to the selected ionic liquid [Bmim][DBP], quantum chemistry calculation method was used to explain the mechanism between ionic liquid [Bmim][DBP] and methanol. The results show that stable hydrogen bonds not only exist between cation and anion in ionic liquid [Bmim][DBP], but also exist between methanol and ionic liquid [Bmim][DBP]. The hydrogen bonds strengthen the interaction among the molecules. The anion [DBP]^- in [Bmim][DBP] and —OH in methanol form a hydrogen bond of 0.1711 nm and the interaction energy is -62.08 kJ/mol. A series of experiments was carried out to determine the effect of ILs/C₄ mass ratio, extraction time and recycle times on the performance of ionic liquid [Bmim][DBP]. The results show that the extraction rate reaches 99.65% under the conditions of ILs/C₄ mass ratio of 1∶2, extraction time of 60 min, temperature of 25 ℃. Furthermore, the extration rate would not decrease after 5 recycles.

Key words: Mixed C₄ hydrocarbon, Ionic liquid, Methanol, Extraction mechanism

CLC Number:

O643

TrendMD:

LI Jianwei,LI Xiang,ZHANG Jie,LEI Zhigang. Mechanism of the Interaction Between Ionic Liquid [Bmim][DBP] and Methanol for Seperation of Mixed C₄/Methanol^†[J]. Chem. J. Chinese Universities, 2018, 39(5): 983.

Figures/Tables 7

Fig.1 Extraction performance of different ILs for CH3OH Note:(A) Extraction efficiency of different ILs; (B) the contents of CH3OH after experiments. t=25 ℃; m(ILs)∶m(oil)=2∶5. a. [Bmim] [Tos]; b. [Bmim] [NTf2]; c. [Bmim] [BF4]; d. [Bmim] [DEP]; e. [Bmim] [HSO4]; f. [Bmim] [TA]; g. [Bmim] [DCA]; h. [Bmim] [Lac]; i. [Bmim] [DBP].

Fig.2 Prediction of solubility of CH3OH in ILs Note:a. [Bmin][Tos]; b. [Bmin][NTf2]; c. [Bmin][BF4]; d. [Bmin][DEP]; e. [Bmin][HSO4]; f. [Bmin][TA]; g. [Bmin][DCA]; h. [Bmin][Lac]; i. [Bmin][DBP].

Fig.3 Optimized geometries at the B3LYP/6-31++G(d,p) level for the extraction systems Note:(A) [Bmim]+; (B) [DBP]-; (C) [Bmim][DBP]; (D) [Bmim]+-CH3OH; (E) [DBP]--CH3OH; (F )[Bmim][DBP]-CH3OH.

Table 1 Total energy for CH3OH and [Bmim][DBP]

Compd.	Total energy/(kJ·mol^-1)	Compd.	Total energy/(kJ·mol^-1)
CH₃OH	3.04×10⁵	[Bmim]⁺ and CH₃OH	1.42×10⁶
[Bmim]⁺	1.11×10⁶	[DBP]^- and CH₃OH	2.82×10⁶
[DBP]^-	2.52×10⁶	[Bmim][DBP] and CH₃OH	3.93×10⁶
[Bmim][DBP]	3.63×10⁶

Fig.4 Effect of ILs/C4 mass ratios on removal rate of CH3OH at 25 ℃

Fig.5 Effect of time on extraction efficiency of CH3OH Note:t=25 ℃; m(ILs)∶m(oil)=2∶5.

Fig.6 Recycling of [Bmim][DBP] in the extraction system Note:t=25 ℃; m(ILs)∶m(oil)=2∶5.

References 27

[1]	Collignon F., Loenders R., Martens J.A., [J]. Catal., 1999, 182, 302—312
[2]	Mike T. John S.; Translated by Du H. S., Shan J. X., Value Stream Mapping, China Communications Press, Beijing, 1999, 35—39
	(杜宏生, 单金秀[译]. 价值流图析, 北京: 人民交通出版社, 1999, 35—39)
[3]	Matouq M., Tagawa T., Goto S., [J]. Chem. Eng. Jpn., 1993, 26, 254—258
[4]	Ma X., Hu C., Guo R., Fang X., Wu H., Jiang Z.Y., Sep. Purif. Technol., 2008, 59, 34—42
[5]	Bitar L.S., Hazbun E. A., Fiel W. [J]., Hydrocarb. Proc., 1984, 63, 63—66
[6]	Wang B., Liu C.J., Wang J. D., Lei Z. K., Hu D. L., Chem. [J]. Chinese Universities, 2012, 33(1), 76—81
	(王斌, 刘晨江, 王吉德, 雷振凯, 胡东林. 高等学校化学学报, 2012, 33(1), 76—81)
[7]	Zhang H., Zhang H.M., Wang L. J, Shen J. Y., Chem. [J]. Chinese Universities, 2016, 37(9), 1660—1668
	(张慧, 张红梅, 王连军, 沈锦优. 高等学校化学学报, 2016, 37(9), 1660—1668)
[8]	Zhang S.J., Xu C. M., Lü X. M., Zhou Q., Ionic Liquids and Green Chemistry, Science Press, Beijing, 2009, 78—99
	(张锁江, 徐春明, 吕兴梅, 周清. 离子液体与绿色化学, 北京: 科学出版社, 2009, 78—99)
[9]	Tong J., Zheng X., Tong J., Qu Y., Liu L., Li H., Chem. Res. Chinese Universities, 2017, 33(5), 828—832
[10]	Zhao Y.M., Cui H. M., Zheng C. Z., Chen X. G., Li C. Y., Chem. Res. Chinese Universities, 2016, 32(1), 112—117
[11]	Huddleston J.G., Rogers R. D., Chem. Commun., 1998, 16, 1765—1766
[12]	Fadeev A.G., Meagher M. M., Chem. Commun., 2001, 3, 295—296
[13]	Khachatryan K.S., Smirnova S. V., Torocheshnikova I. I., Shvedene N. V., Formanovsky A. A., Anal. Bioanal. Chem., 2005, 381, 464—470
[14]	Smirnova S.V., Torocheshnikova I. I., Formanovsky A. A., Pletnev I. V., Anal. Bioanal. Chem., 2004, 378, 1369—1375
[15]	Huddleston J.G., ACS Symposium, 2002, 818, 270—288
[16]	Pereiro A.B., Deive F. J., Esperança J. M. S. S., Rodríguez A., Fluid Phase Equilibr., 2010, 294, 49—53
[17]	Revelli A.L., Mutelet F., Jaubert J., J. Chem. Eng. Data, 2011, 56, 3873—3880
[18]	Marciniak A., Królikowski M., Fluid Phase Equilibr., 2012, 321, 59—63
[19]	Wlazło M., Marciniak A., Fluid Phase Equilibr., 2014, 338, 253—256
[20]	Cai F., Xiao G., [J]. Chem. Thermodyn., 2015, 87, 110—116
[21]	Cammarata L., Kazarian S.G., Salterb P. A., Welton T., Phys. Chem. Chem. Phys., 2001, 3, 5192—5200
[22]	Porter A.R., Liem S. Y., Popelier P. L. A., Phys. Chem. Chem. Phys., 2008, 10, 4240—4248
[23]	Zhang Q.G., Wang N. N., Yu Z. W., J. Phys. Chem. B, 2010, 114, 47—54
[24]	Köddermann T., Wertz C., Heintz A., Ludwig R., ChemPhysChem, 2010, 7, 1944—1949
[25]	Dhumal N.R., Kim H. J., Kiefer J., J. Phys. Chem. A, 2009, 113, 10397—10404
[26]	Becke A.D., [J]. Chem. Phys., 1993, 98, 5648—5653
[27]	Ditchfield R., Hehre W.J., Pople J. A., [J]. Chem. Phys., 1971, 54, 724—728

Mechanism of the Interaction Between Ionic Liquid [Bmim][DBP] and Methanol for Seperation of Mixed C₄/Methanol^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 7

References 27

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	CUI Wei, ZHAO Deyin, BAI Wenxuan, ZHANG Xiaodong, YU Jiang. CO₂ Absorption in Composite of Aprotic Solvent and Iron-based Ionic Liquid [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220120.
[2]	ZHOU Zixuan, YANG Haiyan, SUN Yuhan, GAO Peng. Recent Progress in Heterogeneous Catalysts for the Hydrogenation of Carbon Dioxide to Methanol [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220235.
[3]	PENG Kuilin, LI Guilin, JIANG Chongyang, ZENG Shaojuan, ZHANG Xiangping. Research Progress for the Role of Electrolytes in the CO₂ Electrochemical Reduction [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220238.
[4]	JI Shuangqi, JIN Zhao, GUAN Wenna, PAN Xiangyu, GUAN Tong. Preparation and Chromatographic Performance of Mixed-mode Silica Stationary Phase Modified by Double Cationic Ionic Liquid and Octadecyl Group [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220008.
[5]	BI Gening, XIAO Xiaohua, LI Gongke. Development and Validation of Multiple Physical Fields Coupling Model for Microwave-assisted Extraction [J]. Chem. J. Chinese Universities, 2022, 43(3): 20210739.
[6]	LIU Jie, LI Jinsheng, BAI Jingsen, JIN Zhao, GE Junjie, LIU Changpeng, XING Wei. Constructing a Water-blocking Interlayer Containing Sulfonated Carbon Tubes to Reduce Concentration Polarization in Direct Methanol Fuel Cells [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220420.
[7]	CHANG Sihui, CHEN Tao, ZHAO Liming, QIU Yongjun. Thermal Degradation Mechanism of Bio-based Polybutylactam Plasticized by Ionic Liquids [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220353.
[8]	XU Xiaolong, FANG Lining, LIU Changyu, LIU Minchao, JIA Jianbo. Preparation of Z-type g-C₃N₄/Pt/TiO₂ Nanotube Array Composite Electrode and Its Performance of Photoelectric Oxidation of Methanol [J]. Chem. J. Chinese Universities, 2021, 42(9): 2926.
[9]	LI Jian, YU Mingming, SUN Yuan, FENG Wenhua, FENG Zhaochi, WU Jianfeng. Effect of Aqueous Solution pH on the Oxidation of Methane to Methanol at Low Temperature [J]. Chem. J. Chinese Universities, 2021, 42(3): 776.
[10]	WAN Ren, SONG Fan, PENG Changjun, LIU Honglai. Group Contribution Method for Infinite Dilution Molar Conductivity of Unconventional Ions in Water [J]. Chem. J. Chinese Universities, 2021, 42(12): 3672.
[11]	WANG Man, WANG Xin, ZHOU Jing, GAO Guohua. Efficient Synthesis of Dimethyl Carbonate via Transesterification of Methanol and Ethylene Carbonate Catalyzed by Poly（ionic liquid）s [J]. Chem. J. Chinese Universities, 2021, 42(12): 3701.
[12]	GUO Shujia, WANG Sen, ZHANG Li, QIN Zhangfeng, WANG Pengfei, DONG Mei, WANG Jianguo, FAN Weibin. Regulating the Acid Sites Distribution in ZSM-5 Zeolite and Its Catalytic Performance in the Conversion of Methanol to Olefins [J]. Chem. J. Chinese Universities, 2021, 42(1): 227.
[13]	ZHOU Molin, JIANG Xin, YI Ting, YANG Xiangguang, ZHANG Yibo. Improvement of Interface Stability Between Sulfide Solid Electrolyte Li₁₀GeP₂S₁₂ and Lithium Metal [J]. Chem. J. Chinese Universities, 2020, 41(8): 1810.
[14]	GAO Chong,YU Fengli,XIE Congxia,YU Shitao. Baeyer-Villiger Oxidation of Cyclic Ketones Catalyzed by Amino Alcohol Heteropoly Acid Ionic Liquid ^† [J]. Chem. J. Chinese Universities, 2020, 41(5): 1101.
[15]	GAO Naiwei, MA Qiang, HE Yonglin, WANG Yapei. Green Electronic Devices Based on Ionic Liquids ^† [J]. Chem. J. Chinese Universities, 2020, 41(5): 901.