离子液体用于四氢呋喃-乙醇-水三元共沸物系分离的研究

doi:10.11949/0438-1157.20190844

摘要/Abstract

摘要：

以离子液体1-丁基-3-甲基咪唑二氰胺（[BMIM] [DCA]）为萃取剂，采用流程模拟和机理分析两种方法，对离子液体用于四氢呋喃（THF）-乙醇-水三元共沸物的分离进行了研究。通过COSMO-RS理论，以选择性为性能指标筛选出合适的离子液体[BMIM][DCA]，并且以[BMIM][DCA]为萃取剂，在适合的操作条件下建立了萃取精馏过程，模拟结果表明THF、乙醇和水的质量分数都接近1。通过对[BMIM][DCA]和三种溶质的σ-谱图分析，发现[BMIM][DCA]可分别与三种溶质形成更强的氢键，从而打破三种溶质间的固有氢键，进而消除它们的共沸现象。

关键词: 离子液体, 共沸物, 萃取精馏, 模拟, 机理

Abstract:

Using ionic liquid 1-butyl-3-methylimidazolium dicyandiamide ([BMIM][DCA]) as extractant, the separation of tetrahydrofuran (THF)-ethanol-water ternary azeotrope was studied by process simulation and mechanism analysis. Based on COSMO-RS theory, suitable ionic liquid [BMIM] [DCA] was selected with selectivity as performance index, and the extractive distillation process was established with [BMIM] [DCA] as extractant and suitable operating conditions. The simulation results showed that the mass fraction of THF, ethanol and water was close to 1. Through the analysis of σ-profiles of [BMIM] [DCA] and three solutes, it is found that [BMIM] [DCA] can form stronger hydrogen bonds with three solutes respectively, thus breaking the inherent hydrogen bonds between the three solutes and eliminating their azeotropy.

Key words: ionic liquid, azeotrope, extractive distillation, simulation, mechanism

中图分类号:

TQ 028.3

李文秀, 张羽, 曹颖, 丁忠瀚, 赵思雨, 张弢. 离子液体用于四氢呋喃-乙醇-水三元共沸物系分离的研究[J]. 化工学报, 2020, 71(4): 1676-1682.

Wenxiu LI, Yu ZHANG, Ying CAO, Zhonghan DING, Siyu ZHAO, Tao ZHANG. Study on separation of tetrahydrofuran-ethanol-water ternary azeotrope system by ionic liquid[J]. CIESC Journal, 2020, 71(4): 1676-1682.

图/表 11

图1 萃取精馏工艺流程

Fig.1 Extractive distillation process

表1 离子液体用于三个二元共沸物系的筛选结果

Table 1 Screening results of ionic liquids for three binary azeotrope systems

共沸物系	离子液体	$γ 1, I L ∞$	$γ 2, I L ∞$	$S i j ∞$
THF（1）+乙醇（2）	[BMIM][BF₄]（3）	2.1049	1.7308	1.2161
	[OMIM][BF₄]（3）	0.8355	1.1638	0.7179
	[BMIM][DCA]（3）	1.8449	0.6547	2.8180
THF（1）+水（2）	[BMIM][BF₄]（3）	2.1049	1.6488	1.2766
	[OMIM][BF₄]（3）	0.8355	2.0985	0.3981
	[BMIM][DCA]（3）	1.8449	0.3722	4.9572
乙醇（1）+水（2）	[BMIM][BF₄]（3）	1.9539	1.6488	1.1850
	[OMIM][BF₄]（3）	1.1638	2.0985	0.5546
	[BMIM][DCA]（3）	0.6548	0.3722	1.7591

表1 离子液体用于三个二元共沸物系的筛选结果

Table 1 Screening results of ionic liquids for three binary azeotrope systems

共沸物系	离子液体	$γ 1, I L ∞$	$γ 2, I L ∞$	$S i j ∞$
THF（1）+乙醇（2）	[BMIM][BF₄]（3）	2.1049	1.7308	1.2161
	[OMIM][BF₄]（3）	0.8355	1.1638	0.7179
	[BMIM][DCA]（3）	1.8449	0.6547	2.8180
THF（1）+水（2）	[BMIM][BF₄]（3）	2.1049	1.6488	1.2766
	[OMIM][BF₄]（3）	0.8355	2.0985	0.3981
	[BMIM][DCA]（3）	1.8449	0.3722	4.9572
乙醇（1）+水（2）	[BMIM][BF₄]（3）	1.9539	1.6488	1.1850
	[OMIM][BF₄]（3）	1.1638	2.0985	0.5546
	[BMIM][DCA]（3）	0.6548	0.3722	1.7591

表2 [BMIM][DCA]的临界性质

Table 2 Critical properties of [BMIM][DCA]

IL	$M W$	$P c × 10 - 5 / P a$	$V C / (c m 3 / m o l)$	$Z c$	$T b / K$	$T c / K$	ω
[BMIM][DCA]	205.3	24.4	712	0.2017	783	1035.8	0.8419

表2 [BMIM][DCA]的临界性质

Table 2 Critical properties of [BMIM][DCA]

IL	$M W$	$P c × 10 - 5 / P a$	$V C / (c m 3 / m o l)$	$Z c$	$T b / K$	$T c / K$	ω
[BMIM][DCA]	205.3	24.4	712	0.2017	783	1035.8	0.8419

表3 [BMIM][DCA]的Ridel方程参数

Table 3 Ridel equation parameters of [BMIM][DCA]

$C 1$	$C 2$	$C 3$	$C 4$	$C 5$	$C 6$	$C 7$
117.65	-19738.88	0	0	-12.16	4.29×10^-19	6.00

表3 [BMIM][DCA]的Ridel方程参数

Table 3 Ridel equation parameters of [BMIM][DCA]

$C 1$	$C 2$	$C 3$	$C 4$	$C 5$	$C 6$	$C 7$
117.65	-19738.88	0	0	-12.16	4.29×10^-19	6.00

表4 基于COSMO-RS理论预测的等压水（1）+[BMIM][DCA]（2）二元汽液平衡数据

Table 4 Isobaric VLE data for water (1) + [BMIM][DCA] (2) predicted based on COSMO-RS theory

x₁	x₂	T/K	lnγ₁	.lnγ₂	y₁
0.80	0.20	378.93	0.01920404	-0.02093020	1.00
0.76	0.24	380.35	0.02195992	-0.02733799	1.00
0.72	0.28	381.89	0.02378783	-0.02956523	1.00
0.68	0.32	383.55	0.02480862	-0.02933896	1.00
0.64	0.36	385.36	0.02513711	-0.02771139	1.00
0.60	0.40	387.33	0.02486963	-0.02532826	1.00
0.56	0.44	389.47	0.02408134	-0.02258857	1.00
0.52	0.48	391.81	0.02282665	-0.01973973	1.00
0.48	0.52	394.39	0.02114004	-0.01693459	1.00
0.44	0.56	397.25	0.01903616	-0.01426653	1.00
0.40	0.60	400.44	0.01650838	-0.01179096	1.00
0.36	0.64	404.04	0.01352485	-0.00953905	1.00
0.32	0.68	408.16	0.01002055	-0.00752664	1.00
0.28	0.72	412.96	0.00588240	-0.00575950	1.00
0.24	0.76	418.66	0.00092092	-0.00423743	1.00
0.20	0.80	425.65	-0.00518639	-0.00295660	1.00

表5 溶质-[BMIM][DCA]的NRTL方程参数

Table 5 NRTL equation parameters of solute-[BMIM][DCA]

i组分	j组分	$α i j$	$? g i j / R$	$? g j i / R$
THF（1）	[BMIM][DCA]（2）	0.223	7135.79	145.11
乙醇（1）	[BMIM][DCA]（2）	1.661	183.70	-281.25
水（1）	[BMIM][DCA]（2）	0.3031	-455.17	670.44

表5 溶质-[BMIM][DCA]的NRTL方程参数

Table 5 NRTL equation parameters of solute-[BMIM][DCA]

i组分	j组分	$α i j$	$? g i j / R$	$? g j i / R$
THF（1）	[BMIM][DCA]（2）	0.223	7135.79	145.11
乙醇（1）	[BMIM][DCA]（2）	1.661	183.70	-281.25
水（1）	[BMIM][DCA]（2）	0.3031	-455.17	670.44

表6 流程模拟的条件和结果

Table 6 Conditions and results of process simulation

Unit	EDC1	EDC2	SRC
number of stages	25	50	6
feed stage of FEED	10	23	3
feed stage of IL	2	2
distillate rate/(kmol/h)	30.02	30	39.98
re?ux ratio	1.8	3.9	0.1
column diameter/m	0.78	1.01	3.38
pressure(condenser)×10^-5/Pa	1	1	0.004
condenser duty/MW	-0.7033	-1.6409	-0.5353
reboiler duty/MW	0.9955	2.3410	2.7699
THF purity/%(mass)	100.00
ethanol purity/%(mass)		100.00
water purity/%(mass)			100.00

图2 EDC1的温度和成分分布

Fig.2 Temperature and composition profiles of EDC1

图3 EDC2的温度和成分分布

Fig.3 Temperature and composition profiles of EDC2

图4 SRC的温度和成分分布

Fig.4 Temperature and composition profiles of SRC

图5 THF、乙醇、水、[BMIM]+、[DCA]-的σ-谱图

Fig.5 σ-Profiles for THF, ethanol, H2O, [BMIM]+ and [DCA]-

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