Measurement and correlation of liquid-liquid equilibrium data for n-hexane- isopropanol azeotropic system

doi:10.11949/0438-1157.20191001

Abstract

Abstract:

To provide basic data for the process design and process simulation calculation of solvent extraction and separation of n-hexane-isopropanol mixture, experimental liquid-liquid equilibrium (LLE) data for separation of isopropanol from n-hexane were measured at 30℃ under atmospheric pressure by using dimethyl sulfoxide, 1,4-butanediol, 1,2-propanediol, acetonitrile, furfural and N,N-dimethylformamide as extractants, respectively. The extraction properties of these selected solvents were assessed by the separation factor based on the experimental LLE data. It was found that separation factor were all higher than 1 with above solvents, corroborating that it is feasible to extract isopropanol from n-hexane using the selected extractants. The consistency and reliability of the experimental data were appraised using the Hand equation, and the correlation coefficients of fitting equations were all above 0.98. Furthermore, the non-random two liquids (NRTL) activity coefficient model in Aspen Plus software was utilized to correlate the experimental tie-line compositions, in which the binary interaction parameters between the components were acquired. Subsequently, the corresponding values of phase equilibrium were calculated and compared with the experimental data. As a result, the root mean square deviation (RMSD) between the calculated and experimental compositions was below 1.0%, indicating that the NRTL model can accurately describe the liquid-liquid phase equilibrium of the ternary system.

Key words: phase equilibria, n-hexane, isopropanol, azeotrope, solvent extraction, NRTL model

摘要：

为了给溶剂萃取分离正己烷–异丙醇混合物的过程设计和流程模拟计算提供基础数据，以二甲亚砜、1,4-丁二醇、1,2-丙二醇、乙腈、糠醛和N,N-二甲基甲酰胺为萃取剂，测定了30℃下萃取分离正己烷–异丙醇混合物的液液相平衡数据，并利用分离因子评价不同萃取剂的萃取分离性能。根据Hand方程对实验数据进行一致性和可靠性检验，拟合方程的相关系数都在0.98以上。随后，采用Aspen Plus软件选取NRTL活度系数模型对相平衡数据进行关联，得到相应的二元交互作用参数，并以此计算相应的相平衡组成。结果显示，计算值和实验值的均方根偏差小于1.0%，表明NRTL模型能够准确描述三元体系的液液相平衡。

关键词: 相平衡, 正己烷, 异丙醇, 共沸物, 溶剂萃取, NRTL模型

CLC Number:

O 642.4

Chong YANG, Xufeng LIN, Jinfeng ZHANG, Hong CHEN, Yepeng XIAO, Hui WANG, Lihua CHENG, Xinping OUYANG. Measurement and correlation of liquid-liquid equilibrium data for n-hexane- isopropanol azeotropic system[J]. CIESC Journal, 2020, 71(7): 3009-3017.

杨冲, 林旭枫, 张金锋, 陈宏, 肖业鹏, 王慧, 程丽华, 欧阳新平. 正己烷–异丙醇共沸体系液液相平衡数据测定及关联[J]. 化工学报, 2020, 71(7): 3009-3017.

Figures/Tables 23

References 32

1	Zhu Z Y, Bai W T, Xu Y, et al. Liquid-liquid extraction of methanol from its mixtures with hexane using three imidazolium-based ionic liquids[J]. J. Chem. Thermodyn., 2019, 138: 189-195.
2	赵利霞, 马永, 孙利, 等. 正己烷生产纯化工艺的理论及设备研究进展[J]. 现代化工, 2009, 29(9): 15-20.
	Zhao L X, Ma Y, Sun L, et al. Research progress in theory and equipment for hexane production and purification[J]. Modern Chemical Industry, 2009, 29(9): 15-20.
3	张飞, 薛晓金. 异丙醇浸出棉籽油的研究[J]. 中国油脂, 2008, 33(7): 13-16.
	Zhang F, Xue X J. Isopropanol extraction of cotton seed oil[J]. China Oils and Fats, 2008, 33(7): 13-16.
4	程能林. 溶剂手册[M]. 第五版. 北京: 化学工业出版社, 2015: 106.
	Cheng N L. Solvents Handbook[M]. 5thed. Beijing: Chemical Industry Press, 2015: 106.
5	孙毅, 谢清若, 韦藤幼, 等. 水-乙酸-糠醛三元体系相平衡数据关联与共沸精馏过程模拟[J]. 化工学报, 2011, 62(7): 1800-1807.
	Sun Y, Xie Q R, Wei T Y, et al. VLE correlation and azeotropic distillation simulation for water-acetic acid-furfural ternary system[J]. CIESC Journal, 2011, 62(7): 1800-1807.
6	Chen M Q, Yu N, Cong L, et al. Design and control of a heat pump-assisted azeotropic dividing wall column for EDA/water separation[J]. Ind. Eng. Chem. Res., 2017, 56(34): 9770-9777.
7	Shen W F, Dong L C, Wei S A, et al. Systematic design of an extractive distillation for maximum-boiling azeotropes with heavy entrainers[J]. AIChE J., 2015, 61(11): 3898-3910.
8	Shang X Y, Ma S T, Pan Q, et al. Process analysis of extractive distillation for the separation of ethanol-water[J]. Chem. Eng. Res. Des., 2019, 148: 298-311.
9	胡松, 李进龙, 李木金, 等. 萃取精馏生产高纯度环氧丙烷的工艺研究[J]. 化工学报, 2019, 70(2): 670-677.
	Hu S, Li J L, Li M J, et al. Extractive refining process for production of propylene oxide with high purification[J]. CIESC Journal, 2019, 70(2): 670-677.
10	Modla G, Lang P. Removal and recovery of organic solvents from aqueous waste mixtures by extractive and pressure swing distillation[J]. Ind. Eng. Chem. Res., 2012, 51: 11473-11481.
11	张海永, 刘潜, 刘兴坤, 等. 低温煤焦油中正十二烷-甲苯-苯酚的相平衡及分离[J]. 化工学报, 2018, 69(8): 3479-3487.
	Zhang H Y, Liu Q, Liu X K, et al. Phase equilibrium and separation of n-dodecane-toluene-phenol in low temperature coal tar[J]. CIESC Journal, 2018, 69(8): 3479-3487.
12	陈赟, 吕冉, 熊康宁, 等. 甲基异丙基甲酮-苯酚-对苯二酚-水的液液相平衡数据测定、模型关联及萃取过程模拟[J]. 化工学报, 2018, 69(4): 1299-1306.
	Chen Y, Lü R, Xiong K N, et al. Experimental determination, thermodynamic modeling and process simulation of methyl isopropyl ketone-phenol-hydroquinone-water quaternary systems[J]. CIESC Journal, 2018, 69(4): 1299-1306.
13	Ma S T, Li J F, Li L M, et al. Liquid–liquid extraction of benzene and cyclohexane using sulfolane-based low transition temperature mixtures as solvents: experiments and simulation[J]. Energ. Fuel., 2018, 32(7): 8006-8015.
14	Gomes R S, Mattedi S, Santos G R. Liquid-liquid equilibria data of protic ionic liquid (ethyl-2-hydroxyethylammonium propionate, diethylammonium propionate, or butylammonium propionate) with 1-butanol + water at 298.15 K[J]. J. Chem. Eng. Data, 2019, 64(7): 2915-2922.
15	Zhang Y H, Gao H R, Wang M X, et al. Research on the effect of the solvent structure and group on separation of 1-hexene, benzene, and thiophene[J]. Energ. Fuel., 2019, 33(6): 5162-5172.
16	苏佳伟. 液液萃取分离正己烷-异丙醇混合体系的研究[D]. 南京: 南京师范大学, 2017.
	Su J W. Research of the separation of n-hexane–isopropanol mixed system by liquid-liquid extraction[D]. Nanjing: Nanjing Normal University, 2017.
17	Hand D B. Dineric distribution[J]. J. Phys. Chem., 1930, 34(9): 1961-2000.
18	Renon H, Prausnitz J M. Local compositions in thermodynamic excess functions for liquid mixtures[J]. AIChE J., 1968, 14(1): 135-144.
19	Dai F F, Xin K, Song Y H, et al. Liquid-liquid equilibria for the ternary system containing 1-butanol + methoxy(methoxymethoxy)methane + water at temperatures of 303.15, 323.15 and 343.15 K[J]. Fluid Phase Equilib., 2016, 409: 466-471.
20	Dai F F, Xin K, Song Y H, et al. Liquid–liquid equilibria for the extraction of phenols from alkane using ethylene glycol[J]. Fluid Phase Equilib., 2016, 419: 50-56.
21	Liu H, Cui P, Xin K, et al. Experimental determination and correlation of liquid-liquid equilibria for water + cyclohexanone + solvents (toluene or p-xylene) ternary systems at 303.15 and 323.15 K under 101.3 kPa[J]. J. Chem. Eng. Data, 2017, 62: 2367-2373.
22	Mokhtarani B, Musavi J, Parvini M, et al. Ternary (liquid–liquid) equilibria of nitrate based ionic liquid+alkane+benzene at 298.15 K: experiments and correlation[J]. Fluid Phase Equilib., 2013, 341: 35-41.
23	Marciniak A, Królikowski M. Ternary (liquid+liquid) equilibria of {trifluorotris (perfluoroethyl) phosphate based ionic liquids+thiophene+heptane}[J]. J. Chem. Thermodyn., 2012, 49: 154-158.
24	汪勤, 张冰剑, 何畅, 等. 环丁砜萃取精馏过程模拟分析及工艺参数优化[J]. 化工学报, 2017, 68(5): 1969-1976.
	Wang Q, Zhang B J, He C, et al. Process simulation and optimization of sulfolane extractive distillation[J]. CIESC Journal, 2017, 68(5): 1969-1976.
25	庄志海, 张建强, 刘殿华. 聚甲氧基二甲醚+水+正己烷三元体系的液液相平衡[J]. 化工学报, 2016, 67(9): 3545-3551.
	Zhuang Z H, Zhang J Q, Liu D H. Liquid-liquid equilibria for ternary systems polyoxymethylene dimethyl ethers + water + n-hexane[J]. CIESC Journal, 2016, 67(9): 3545-3551.
26	Toledo I E P, Ferreira-Pinto L, Voll F A P, et al. Liquid–liquid equilibrium of the system {peanut biodiesel + glycerol + ethanol} at atmospheric pressure[J]. J. Chem. Eng. Data, 2019, 64(5): 2207-2212.
27	时米东, 王利平, 何高银, 等. 低浓度甲缩醛水溶液–萃取剂液液相平衡数据的测定与关联[J]. 天然气化工(C1化学与化工), 2018, 43(1): 34-39+46.
	Shi M D, Wang L P, He G Y, et al. Measurement and correlation of liquid-liquid equilibria data for low concentrated methylal aqueous solution and extractants[J]. Natural Gas Chemical Industry, 2018, 43(1): 34-39+46.
28	崔鹏, 刘海, 于雪敏, 等. 水-环己酮-甲基异丁基酮液液萃取相平衡数据的测定与关联[J]. 物理化学学报, 2018, 34(1): 65-72.
	Cui P, Liu H, Yu X M, et al. Measurement and correlation of liquid-liquid equilibrium data for the water + cyclohexanone + methyl isobutyl ketone ternary system[J]. Acta Physico-Chimica Sinica, 2018, 34(1): 65-72.
29	Yang C, Yu X M, Wang L P, et al. Experimental measurement and thermodynamic modelling of liquid-liquid equilibria for the separation of 1,2-dichloroethane from cyclohexane using various extractants[J]. J. Mol. Liq., 2018, 252: 263-270.
30	Naik P K, Paul S, Banerjee T. Liquid-liquid equilibria measurements for the extraction of poly aromatic nitrogen hydrocarbons with a low cost deep eutectic solvent: experimental and theoretical insights[J]. J. Mol. Liq., 2017, 243: 542-552.
31	Al-Tuwaim M S, Alkhaldi K H A E, Fandary M S, et al. Extraction of propylbenzene from its mixtures with heptadecane using 4-methyl-N-butylpyridinium tetrafluoroborate[J]. Fluid Phase Equilib., 2012, 315: 21-28.
32	冯艺荣, 盖恒军, 郭凯, 等. 甲基戊烯酮-水-邻苯二酚三元物系液液相平衡数据的测定与关联[J]. 化工学报, 2017, 68(3): 848-853.
	Feng Y R, Gai H J, Guo K, et al. Measurement and correlation of liquid-liquid equilibrium data for mesityl oxide-water-catechol ternary system[J]. CIESC Journal, 2017, 68(3): 848-853.

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试剂名称	CAS^①	纯度/%(mass)	生产厂家
正己烷	110-54-3	＞99	上海阿拉丁生化科技股份有限公司
异丙醇	67-63-0	≥99.7	国药集团化学试剂有限公司
二甲亚砜	67-68-5	≥99.0	国药集团化学试剂有限公司
1,4-丁二醇	110-63-4	≥99.0	国药集团化学试剂有限公司
1,2-丙二醇	57-55-6	≥99.0	国药集团化学试剂有限公司
乙腈	75-05-8	≥99.0	国药集团化学试剂有限公司
糠醛	98-01-1	≥99.0	国药集团化学试剂有限公司
N,N-二甲基甲酰胺	68-12-2	≥99.5	国药集团化学试剂有限公司
1,4-二氧六环	123-91-1	≥99.0	上海阿拉丁生化科技股份有限公司
无水乙醇	64-17-5	≥99.7	广州市东红实业发展有限公司
氢气	——	99.999	茂名市民兴气体有限公司

试剂名称	CAS^①	纯度/%(mass)	生产厂家
正己烷	110-54-3	＞99	上海阿拉丁生化科技股份有限公司
异丙醇	67-63-0	≥99.7	国药集团化学试剂有限公司
二甲亚砜	67-68-5	≥99.0	国药集团化学试剂有限公司
1,4-丁二醇	110-63-4	≥99.0	国药集团化学试剂有限公司
1,2-丙二醇	57-55-6	≥99.0	国药集团化学试剂有限公司
乙腈	75-05-8	≥99.0	国药集团化学试剂有限公司
糠醛	98-01-1	≥99.0	国药集团化学试剂有限公司
N,N-二甲基甲酰胺	68-12-2	≥99.5	国药集团化学试剂有限公司
1,4-二氧六环	123-91-1	≥99.0	上海阿拉丁生化科技股份有限公司
无水乙醇	64-17-5	≥99.7	广州市东红实业发展有限公司
氢气	——	99.999	茂名市民兴气体有限公司

仪器名称	型号	生产厂家
气相色谱仪	GC9790	浙江福立分析仪器有限公司
电子天平	CP512	广州泸瑞明仪器有限公司
低温恒温水槽	DC-3010	上海比朗仪器制造有限公司
烘箱	DHG-9076A	上海精宏实验设备有限公司
磁力搅拌器	FK-2A	腾科科学仪器有限公司
微量进样器	1 μl	上海高鸽工贸有限公司

仪器名称	型号	生产厂家
气相色谱仪	GC9790	浙江福立分析仪器有限公司
电子天平	CP512	广州泸瑞明仪器有限公司
低温恒温水槽	DC-3010	上海比朗仪器制造有限公司
烘箱	DHG-9076A	上海精宏实验设备有限公司
磁力搅拌器	FK-2A	腾科科学仪器有限公司
微量进样器	1 μl	上海高鸽工贸有限公司

Extraction phase			Raffinate phase			S
w₁	w₂	w₃	w₁	w₂	w₃	S
0.0182	0	0.9818	0.9984	0	0.0016	—
0.0246	0.0518	0.9236	0.9818	0.0026	0.0156	795.14
0.0429	0.1040	0.8531	0.9757	0.0064	0.0179	369.58
0.0630	0.1566	0.7804	0.9644	0.0118	0.0238	203.15
0.0888	0.1998	0.7114	0.9505	0.0187	0.0308	114.36
0.1104	0.2409	0.6487	0.9410	0.0271	0.0319	75.77
0.1675	0.2691	0.5634	0.9086	0.0414	0.0500	35.26
0.2272	0.2953	0.4775	0.8825	0.0592	0.0583	19.38