Multi-objective optimization design of triple-column pressure-swing distillation for separating ternary azeotropic mixture tetrahydrofuran/methanol/ethanol by thermodynamic topology theory

doi:10.16085/j.issn.1000-6613.2025-0567

Abstract

Abstract:

The ternary system of tetrahydrofuran (THF), methanol (MeOH), and ethanol (EtOH), characterized by one distillation boundary and two azeotropic points, presents significant challenges for conventional distillation separation. To overcome this limitation, the variation trend of the phase diagram and the movement direction of azeotropic point of the ternary system THF/MeOH/EtOH under different pressures were investigated. Based on thermodynamic topological theories such as distillation boundaries and residual curves, the feasibility of pressure-swing distillation separation of ternary azeotropic mixtures THF/MeOH/EtOH was analyzed. Furthermore, based on thermodynamic topological theories such as residual curves, component equilibrium lines, and distillation boundaries, process conceptual design was carried out for two pressure-swing distillation separation sequences. Through COM technology integration between Aspen Plus and Matlab, a multi-objective particle swarm optimization (MOPSO) algorithm was implemented to optimize both sequences, with economic and safety metrics serving as objective functions. The results indicated that thermodynamic topological theory analysis could quickly realize the conceptual design of pressure-swing distillation separation of ternary azeotropic mixtures. Compared to the EtOH-THF-MeOH separation sequence, the EtOH-MeOH-THF separation sequence exhibited strong advantages in terms of economic and safety performance.

Key words: pressure-swing distillation, optimal design, ternary azeotropic mixture, optimization, safety, separation

摘要：

四氢呋喃（THF）、甲醇（MeOH）和乙醇（EtOH）三元体系包含一条精馏边界与两个共沸点，导致采用常规精馏技术分离尤为困难。为了解决这一问题，本文探究了三元体系THF/MeOH/EtOH在不同压力下相图的变化趋势及共沸点的移动方向，基于精馏边界、剩余曲线等热力学拓扑理论分析变压精馏分离三元共沸混合物THF/MeOH/EtOH的可行性。进一步地，结合剩余曲线、组分平衡线和精馏边界等热力学拓扑理论对两种变压精馏分离序列进行工艺概念设计。最后，通过组件对象模型（COM）技术连接Aspen Plus和Matlab，采用多目标粒子群算法以经济和安全指标为目标函数对不同分离序列进行优化设计。结果表明：热力学拓扑理论分析可以快速实现变压精馏分离三元共沸混合物的概念设计；相比于EtOH-THF-MeOH分离序列，EtOH-MeOH-THF分离序列在经济和安全性能方面表现出了较强的优势。

关键词: 变压精馏, 优化设计, 三元共沸混合物, 优化, 安全, 分离

CLC Number:

TQ223.2

YANG Ao, DENG Wei, LI Yong, LUO Jing, WANG Zilin, ZHANG Jun, SHEN Weifeng. Multi-objective optimization design of triple-column pressure-swing distillation for separating ternary azeotropic mixture tetrahydrofuran/methanol/ethanol by thermodynamic topology theory[J]. Chemical Industry and Engineering Progress, 2025, 44(8): 4582-4593.

杨傲, 邓苇, 黎勇, 罗婧, 王梓霖, 张俊, 申威峰. 基于热力学拓扑理论的三塔变压精馏分离四氢呋喃/甲醇/乙醇多目标优化设计[J]. 化工进展, 2025, 44(8): 4582-4593.

Figures/Tables 18

References 27

[1]	LI Guoxuan, LIU Shengli, YU Gangqiang, et al. Extractive distillation using ionic liquids-based mixed solvents combined with dividing wall column[J]. Separation and Purification Technology, 2021, 269: 118713.
[2]	HUANG Weiqing, XIANG Dong. Optimal design framework and techno-economic-environmental assessment for efficient solvent recovery separation of ethyl acetate and methanol[J]. Separation and Purification Technology, 2021, 260: 118210.
[3]	SHOLL David S, LIVELY Ryan P. Seven chemical separations to change the world[J]. Nature, 2016, 532(7600): 435-437.
[4]	YANG Ao, WANG Wenhe, SUN Shirui, et al. Sustainable design and multi-objective optimization of eco-efficient extractive distillation with single and double entrainer(s) for separating the ternary azeotropic mixture tetrahydrofuran/ethanol/methanol[J]. Separation and Purification Technology, 2022, 285: 120413.
[5]	SUN Shirui, Liping LYU, YANG Ao, et al. Extractive distillation: Advances in conceptual design, solvent selection, and separation strategies[J]. Chinese Journal of Chemical Engineering, 2019, 27(6): 1247-1256.
[6]	ZHANG Yinrui, WU Tsai-Wei, I-Lung CHIEN. Energy-efficient heterogeneous azeotropic distillation coupling with pressure swing distillation for the separation of IPA/DIPE/water mixture[J]. Journal of the Taiwan Institute of Chemical Engineers, 2022, 130: 103843.
[7]	YANG Ao, KONG ZONG yang, SUNARSO Jaka. Design and optimisation of novel hybrid side-stream reactive-extractive distillation for recovery of isopropyl alcohol and ethyl acetate from wastewater[J]. Chemical Engineering Journal, 2023, 451: 138563.
[8]	LIANG Shisheng, CAO Yujuan, LIU Xingzhen, et al. Insight into pressure-swing distillation from azeotropic phenomenon to dynamic control[J]. Chemical Engineering Research and Design, 2017, 117: 318-335.
[9]	ZHU Zhaoyou, XU Dongfang, LIU Xingzhen, et al. Separation of acetonitrile/methanol/benzene ternary azeotrope via triple column pressure-swing distillation[J]. Separation and Purification Technology, 2016, 169: 66-77.
[10]	黄旭, 罗祎青, 袁希钢. 带共沸的乙醇/乙酸乙酯/2-丁酮三元物系变压精馏分离过程及其参数优化[J]. 化工学报, 2018, 69(5): 2089-2099.
	HUANG Xu, LUO Yiqing, YUAN Xigang. Separation of C₂H₅OH/C₄H₈O₂-3/ C₄H₈O-3 ternary mixture with azeotropes by pressure swing distillation and its parameter optimization[J]. CIESC Journal, 2018, 69(5): 2089-2099.
[11]	YANG Ao, SHEN Weifeng, WEI Shunan, et al. Design and control of pressure-swing distillation for separating ternary systems with three binary minimum azeotropes[J]. AIChE Journal, 2019, 65(4): 1281-1293.
[12]	向晟, 王超, 庄钰, 等. 变压精馏分离乙酸甲酯-甲醇-乙酸乙酯体系的设计与控制[J]. 化工进展, 2022, 41(8): 4065-4076.
	XIANG Sheng, WANG Chao, ZHUANG Yu, et al. Design and control of pressure-swing distillation for separating methyl acetate-methanol-ethyl acetate azeotropic system[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4065-4076.
[13]	高晓新, 陆凯锐, 陈群, 等. 化工专业三元共沸物分离实验与模拟探究[J]. 实验室研究与探索, 2021, 40(8): 186-189.
	GAO Xiaoxin, LU Kairui, CHEN Qun, et al. Research on the separation experiment and simulation of ternary azeotrope in chemical engineering[J]. Research and Exploration In Laboratory, 2021, 40(8): 186-189.
[14]	KIVA V N, HILMEN E K, SKOGESTAD S. Azeotropic phase equilibrium diagrams: A survey[J]. Chemical Engineering Science, 2003, 58(10): 1903-1953.
[15]	ZHU Jiaxing, YANG Ao, ZHANG Hao, et al. Pressure-swing heterogeneous azeotropic distillation for energy-efficient recovery of ethyl acetate and methanol from wastewater with expanded feed composition range[J]. Computers & Chemical Engineering, 2025, 194: 108956.
[16]	李鑫, 王维, 张羽, 等. 分离乙酸乙酯+乙醇+水体系: 离子液体筛选、汽液相平衡和过程模拟[J]. 化工进展, 2025, 44(1): 75-85.
	LI Xin, WANG Wei, ZHANG Yu, et al. Separation of ethyl acetate+ethanol+water system: Ionic liquids screening, vapor liquid equilibrium and process simulation[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 75-85.
[17]	HU Yi, SHI Tao, YANG Ao, et al. Investigation on the molecular interaction mechanisms of ionic liquid-organic mixed entrainers for azeotrope separation in extractive distillation[J]. Separation and Purification Technology, 2025, 363: 132262.
[18]	YANG Ao, SU Yang, SUN Shirui, et al. Towards sustainable separation of the ternary azeotropic mixture based on the intensified reactive-extractive distillation configurations and multi-objective particle swarm optimization[J]. Journal of Cleaner Production, 2022, 332: 130116.
[19]	SUN Shirui, YANG Ao, CHANG Chenglin, et al. Improved multiobjective particle swarm optimization integrating mutation and changing inertia weight strategy for optimal design of the extractive single and double dividing wall column[J]. Industrial & Engineering Chemistry Research, 2023, 62(43): 17923-17936.
[20]	LUYBEN William L. Principles and case studies of simultaneous design[M]. New York: John Wiley & Sons Inc., 2011.
[21]	杨林睿, 刘鉴漪, 李玲, 等. 苯/环己烷/环己烯萃取精馏过程的流程设计与节能[J]. 化工学报, 2025, 76(2): 731-743.
	YANG Linrui, LIU Jianqi, LI Ling, et al. Process design and energy saving for benzene/cyclohexane/cyclohexene extractive distillation process[J]. CIESC Journal, 2025, 76(2): 731-743.
[22]	YANG Ao, SU Yang, SHI Tao, et al. Energy-efficient recovery of tetrahydrofuran and ethyl acetate by triple-column extractive distillation: Entrainer design and process optimization[J]. Frontiers of Chemical Science and Engineering, 2022, 16(2): 303-315.
[23]	马长金, 李腾, 安维中, 等. 碳酸丙烯酯为萃取剂萃取精馏分离碳酸二甲酯-甲醇流程模拟与经济性评价[J]. 化工进展, 2024, 43(12): 6608-6614.
	MA Changjin, LI Teng, AN Weizhong, et al. Simulation and economic evaluation of separating dimethyl carbonate-methanol by extractive distillation with propylene carbonate as solvent[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 6608-6614.
[24]	孔洁, 李沅欣, 孙兰义. 萃取精馏分离丙酮-正庚烷的模拟与控制[J]. 化工进展, 2025, 44(3): 1253-1262.
	KONG Jie, LI Yuanxin, SUN Lanyi. Simulation and control of acetone/n-heptane separation by extractive distillation[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1253-1262.
[25]	ZHU Jiaxing, HAO Lin, WEI Hongyuan. Sustainable concept design including economic, environment and inherent safety criteria: Process intensification-reactive pressure swing distillation[J]. Journal of Cleaner Production, 2021, 314: 127852.
[26]	SUN Shirui, FU Liang, YANG Ao, et al. An intensified energy-saving architecture for side-stream extractive distillation of four-azeotrope mixtures considering economic, environmental and safety criteria simultaneously[J]. Separation and Purification Technology, 2023, 310: 123132.
[27]	杨傲, 王文和, 米红甫, 等. 基于Aspen Plus 的化工过程安全仿真实训课程设计与探索[J]．实验技术与管理, 2023, 40(9): 150-156.
	YANG Ao, WANG Wenhe, MI Hongfu, et al. Design and exploration of chemical process safety simulation training course based on Aspen Plus[J]. Experimental Technology and Management, 2023, 40(9): 150-156.

组分	ΔH_C/kcal·mol^-1	LFL₂₅/%·%^-1	UFL₂₅/%·%^-1
甲醇（MeOH）	-152.431	6.0	50.0
四氢呋喃（THF）	-555.317	2.0	11.8
乙醇（EtOH）	-294.975	3.1	27.7

组分	ΔH_C/kcal·mol^-1	LFL₂₅/%·%^-1	UFL₂₅/%·%^-1
甲醇（MeOH）	-152.431	6.0	50.0
四氢呋喃（THF）	-555.317	2.0	11.8
乙醇（EtOH）	-294.975	3.1	27.7

混合物	相对误差类型	NRTL相对误差/%	UNIQUAC相对误差/%
THF-MeOH	温度	0.14	0.17
THF-MeOH	气相摩尔分数	1.35	1.39
THF-EtOH	温度	0.17	0.17
THF-EtOH	气相摩尔分数	2.52	2.57
MeOH-EtOH	温度	0.19	0.19
MeOH-EtOH	气相摩尔分数	2.86	2.85

混合物	相对误差类型	NRTL相对误差/%	UNIQUAC相对误差/%
THF-MeOH	温度	0.14	0.17
THF-MeOH	气相摩尔分数	1.35	1.39
THF-EtOH	温度	0.17	0.17
THF-EtOH	气相摩尔分数	2.52	2.57
MeOH-EtOH	温度	0.19	0.19
MeOH-EtOH	气相摩尔分数	2.86	2.85

组分i	组分j	数据来源	温度单位	a_ij	a_ji	b_ij	b_ji	c_ij
THF	EtOH	APV121 VLE-IG	℉	2.3225	-2.777	-944.83548	1630.3302	0.3
MeOH	THF	APV121 VLE-IG	℉	0	0	113.58918	403.47126	0.3
MeOH	EtOH	APV121 VLE-IG	℉	4.7119	-2.3127	-2092.13082	870.91848	0.3