Advanced separation processes of azeotropes based on multi-scale solvent screening and multi-performance evaluation

YAN Lei; XU Pan; LI Guoxuan; XIA Li; SUN Xiaoyan; WANG Lili; XIANG Shuguang

doi:10.11949/0438-1157.20260272

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Advanced separation processes of azeotropes based on multi-scale solvent screening and multi-performance evaluation

更新时间：2026-07-15

- Advanced separation processes of azeotropes based on multi-scale solvent screening and multi-performance evaluation
- CIESC Journal (2026)
- 作者机构：
  
  青岛科技大学化工学院，山东省化工过程模拟与优化工业软件重点实验室，山东青岛 266042
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20260272
  CLC： TQ 028
- Received：28 February 2026，
  
  Revised：2026-07-13，
  
  Accepted：15 July 2026，
- 稿件说明：
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YAN Lei, XU Pan, LI Guoxuan, et al. Advanced separation processes of azeotropes based on multi-scale solvent screening and multi-performance evaluation[J/OL]. CIESC Journal, 2026.
DOI：

YAN Lei, XU Pan, LI Guoxuan, et al. Advanced separation processes of azeotropes based on multi-scale solvent screening and multi-performance evaluation[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260272.

摘要

针对传统单一相对挥发度筛选方法难以揭示萃取剂选择性分子机制及潜在共沸风险的问题，本文采用一种多尺度萃取剂筛选策略，将宏观相对挥发度分析与微观 σ-profile 表面电荷密度分布及分子间相互作用能计算相结合。该方法不仅能够评价萃取剂对汽液平衡行为的调控能力，还可从氢键供受体特征和分子间作用强度角度阐明萃取剂的选择性来源，从而提高萃取剂筛选的可靠性和机理可解释性。研究发现，由于N-甲基甲酰胺(NMF)与组分间存在强相互作用且表现出优异的分离性能，其被确定为分离六甲基二硅氧烷(HMDSO)/1

2-二氯乙烷(DCE)共沸混合物的高效萃取剂。为进一步提高能量利用效率，本文提出并系统优化了热集成萃取精馏工艺。通过权衡经济与环境目标，对塔板数、进料位置、回流比及萃取剂流量等关键工艺参数进行了优化。与无热集成的常规萃取精馏工艺相比，热集成工艺的年度总成本(TAC)降低了1.24%，运行成本降低了1.67%。优化后的热集成流程其TAC为178万美元/年，运行成本为132万美元/年，证明了该工艺在高效、可持续共沸分离方面的潜力。

Abstract

To address the limitations of conventional screening methods based solely on relative volatility

which are insufficient to reveal the molecular origin of entrainer selectivity and potential azeotrope-formation risks

this study adopts a multiscale entrainer screening strategy that integrates macroscopic relative volatility analysis with microscopic σ-profile surface charge density distributions and intermolecular interaction energy calculations. This approach not only evaluates the ability of an entrainer to regulate vapor-liquid equilibrium behavior

but also elucidates the origin of entrainer selectivity in terms of hydrogen-bond donor/acceptor characteristics and intermolecular interaction strength

thereby improving the reliability and mechanistic interpretability of entrainer screening. N-methylformamide (NMF) was identified as a highly effective entrainer for the separation of the Hexamethyldisiloxane (HMDSO)/1

2-dichloroethane (DCE) azeotropic mixture due to its strong interaction with both components and superior separation performance. To further enhance energy efficiency

a heat-integrated extractive distillation process was proposed and systematically optimized. The key process parameters including the number of trays

feed stage locations

reflux ratio

and entrainer flow rate were optimized by balancing economic and environmental objectives. Compared with the conventional extractive distillation process without heat integration

the heat-integrated process reduced the total annual cost (TAC) by 1.24% and the operating cost by 1.67%. The optimized heat-integrated flowsheet resulted in a TAC of $1.78 million/year and an operating cost of $1.32 million/year

demonstrating its potential for efficient and sustainable azeotropic separation.

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references

Quilcaille Y , Gudmundsson L , Schumacher D L , et al . Systematic attribution of heatwaves to the emissions of carbon majors [J ] . Nature , 2025 , 645 ( 8080 ): 392 - 398 .

Li C Y , Wang L L , Chen C , et al . Exergy, economic, and climate performance evaluation of an efficient clean cogeneration system driven by low-temperature waste-heat [J ] . Journal of Cleaner Production , 2023 , 403 : 136773 .

Wang L L , Niu B W , Xia L , et al . Towards on energy-saving separation of ethylene glycol mixture from production plants based on energy, exergy, economic, environmental, exergoeconomic, and exergoenvironmental analyses [J ] . Journal of Cleaner Production , 2022 , 377 : 134388 .

曹健 , 钱红亮 , 冯新 , 等 . 热力学视角下的碳中和三问 [J ] . 化工学报 , 2024 , 75 ( 11 ): 4378 - 4384 .

Cao J , Qian H L , Feng X , et al . Three questions on carbon neutrality from the perspective of thermodynamics [J ] . CIESC Journal , 2024 , 75 ( 11 ): 4378 - 4384 .

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 L R , Liu J Y , Li L , et al . Process design and energy saving for benzene/cyclohexane/cyclohexene extractive distillation process [J ] . CIESC Journal , 2025 , 76 ( 2 ): 731 - 743 .

武庭宇 , 王超 , 秦余涛 , 等 . 乙酸乙酯/乙醇/水体系预分离萃取精馏工艺研究 [J ] . 化工学报 , 2023 , 74 ( 11 ): 4578 - 4586 .

Wu T Y , Wang C , Qin Y T , et al . Study of extractive distillation processes with preconcentration for separating ethyl acetate/ethanol/water azeotropic mixture [J ] . CIESC Journal , 2023 , 74 ( 11 ): 4578 - 4586 .

Wang Z , Wu Q M , Wang Y Y , et al . Process design and energy, exergy, economic, and environmental analysis of mixed entrainer extractive distillation separation of wastewater containing tetrahydrofuran and ethanol [J ] . Chemical Engineering Science , 2025 , 309 : 121432 .

Luyben W L . Pressure-swing distillation for minimum- and maximum-boiling homogeneous azeotropes [J ] . Industrial & Engineering Chemistry Research , 2012 , 51 ( 33 ): 10881 - 10886 .

Li H X , Han Z L , Zheng X Y , et al . Multiobjective optimization and 4E analysis of extractive pressure swing distillation process based on computer-aided extractant design [J ] . Industrial & Engineering Chemistry Research , 2025 , 64 ( 44 ): 21167 - 21182 .

Li G X , Liu S L , Yu G Q , et al . Extractive distillation using ionic liquids-based mixed solvents combined with dividing wall column [J ] . Separation and Purification Technology , 2021 , 269 : 118713 .

Zhu Z Y , Wang L L , Ma Y X , et al . Separating an azeotropic mixture of toluene and ethanol via heat integration pressure swing distillation [J ] . Computers & Chemical Engineering , 2015 , 76 : 137 - 149 .

王俐智 , 杭钱程 , 郑叶玲 , 等 . 离子液体萃取剂萃取精馏分离丙酸甲酯+甲醇共沸物 [J ] . 化工学报 , 2023 , 74 ( 9 ): 3731 - 3741 .

Wang L Z , Hang Q C , Zheng Y L , et al . Separation of methyl propionate + methanol azeotrope using ionic liquid entrainers [J ] . CIESC Journal , 2023 , 74 ( 9 ): 3731 - 3741 .

Cismondi M , Michelsen M . Automated calculation of complete Pxy and Txy diagrams for binary systems [J ] . Fluid Phase Equilibria , 2007 , 259 ( 2 ): 228 - 234 .

Modla G , Lang P , Denes F . Feasibility of separation of ternary mixtures by pressure swing batch distillation [J ] . Chemical Engineering Science , 2010 , 65 ( 2 ): 870 - 881 .

Wasylkiewicz S K , Kobylka L C , Castillo F J L . Pressure sensitivity analysis of azeotropes [J ] . Industrial & Engineering Chemistry Research , 2003 , 42 ( 1 ): 207 - 213 .

Li H W , Andersen T R , Gani R , et al . Operating pressure sensitivity of DistillationControl structure consequences [J ] . Industrial & Engineering Chemistry Research , 2006 , 45( 25 ) 8310 - 8318 .

Wang L L , Zhang X X , Li C Y , et al . Superefficient separation of HFC-245fa/HF using extractive distillation: From computational thermodynamics to process assessment [J ] . Separation and Purification Technology , 2023 , 307 : 122663 .

Zheng Y Z , Jiang Y X , Zhou Y , et al . The molecular nature of the eliminating azeotropy of dimethyl carbonate-ethanol system by ionic liquid entrainer [J ] . Separation and Purification Technology , 2023 , 305 : 122420 .

Hu Y J , Li F H , Wei S N , et al . Design and optimization of the efficient extractive distillation process for separating the binary azeotropic mixture methanol-acetone based on the quantum chemistry and conceptual design [J ] . Separation and Purification Technology , 2020 , 242 : 116829 .

张缘良 , 栾昕奇 , 苏伟格 , 等 . 离子液体复合萃取剂选择性萃取尼古丁的研究及DFT计算 [J ] . 化工学报 , 2023 , 74 ( 7 ): 2947 - 2956 .

Zhang Y L , Luan X Q , Su W G , et al . Study on selective extraction of nicotine by ionic liquids composite extractant and DFT calculation [J ] . CIESC Journal , 2023 , 74 ( 7 ): 2947 - 2956 .

Zhang Y L , Qiu X M , Zhang H R , et al . Quantum chemistry of solvent selectivity and economic, exergy and environment analysis of extractive distillation process for separating binary azeotropic mixture [J ] . Journal of the Taiwan Institute of Chemical Engineers , 2021 , 129 : 180 - 188 .

Xu P , Shang Z J , Li G X , et al . Biomethane purification with quaternary ammonium salts-based deep eutectic solvents: Experiment and computational thermodynamics [J ] . Separation and Purification Technology , 2023 , 318 : 123980 .

李春利 , 张静 , 方静 . 常压下六甲基二硅醚-1,2-二氯乙烷汽液平衡数据的测定与关联 [J ] . 河北工业大学学报 , 2013 , 42 ( 3 ): 33 - 37 .

Li C L , Zhang J , Fang J . Determination and correlation of vapor-liquid equilibrium data for hexamethyl disiloxane-ethylene dichloride system at 101.3 kPa [J ] . Journal of Hebei University of Technology , 2013 , 42 ( 3 ): 33 - 37 .

Brouwer T , Schuur B . Biobased entrainer screening for extractive distillation of acetone and diisopropyl ether [J ] . Separation and Purification Technology , 2021 , 270 : 118749 .

Zhang H R , Wang S , Tang J X , et al . Multi-objective optimization and control strategy for extractive distillation with dividing-wall column/pervaporation for separation of ternary azeotropes based on mechanism analysis [J ] . Energy , 2021 , 229 : 120774 .

Lin S T , Sandler S I . A priori phase equilibrium prediction from a segment contribution solvation model [J ] . Industrial & Engineering Chemistry Research , 2002 , 41( 5 ) 899 - 913 .

Wang S , Sandler S I , Chen C C . Refinement of COSMO–SAC and the applications [J ] . Industrial & Engineering Chemistry Research , 2007 , 46 ( 22 ): 7275 - 7288 .

Tu W H , Bai L , Zeng S J , et al . An ionic fragments contribution-COSMO method to predict the surface charge density profiles of ionic liquids [J ] . Journal of Molecular Liquids , 2019 , 282 : 292 - 302 .

Zhu Z Y , Geng X L , He W , et al . Computer-aided screening of ionic liquids as entrainers for separating methyl acetate and methanol via extractive distillation [J ] . Industrial & Engineering Chemistry Research , 2018 , 57 ( 29 ): 9656 - 9664 .

Sun Z , Su L , Yao D D , et al . Selective separation of HNO 3 and HCl by extraction: the investigation on the noncovalent interaction between extractants and acids by density functiona l theory [J ] . The Journal of Physical Chemistry. B , 2021 , 125 ( 4 ): 1214 - 1226 .

Li G X , Gui C M , Zhu R S , et al . Deep eutectic solvents for efficient capture of cyclohexane in volatile organic compounds: Thermodynamic and molecular mechanism [J ] . AIChE Journal , 2022 , 68 ( 3 ): e17535 .

Liu Q H , Li G X , Gui C M , et al . Solvents evaluation for extraction of polycyclic aromatics from FCC diesel: Experimental and computational thermodynamics [J ] . Chemical Engineering Science , 2022 , 264 : 118205 .

Cheng Y Q , Yang B , Li G X , et al . Transesterification reactive extractive distillation process using ionic liquids as entrainers: From molecular insights to process integration [J ] . Separation and Purification Technology , 2022 , 301 : 122002 .

Yang B , Cheng Y Q , Chen K , et al . Ester hydrolysis to alcohol using a combined reactive and extractive distillation with ionic liquids-based mixed solvents [J ] . Fuel , 2022 , 327 : 125131 .

Li G X , Liu Q H , Gui C M , et al . Thermodynamic and molecular insights into natural gas dehydration using choline chloride-based deep eutectic solvents [J ] . AIChE Journal , 2022 , 68 ( 7 ): e17662 .

Yu G Q , Xu R N , Wu B , et al . Molecular thermodynamic and dynamic insights into gas dehydration with imidazolium-based ionic liquids [J ] . Chemical Engineering Journal , 2021 , 416 : 129168 .

Boys S F , Bernardi F . The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors [J ] . Molecular Physics , 2002 , 100 ( 1 ): 65 - 73 .

Li G X , Chen K , Lei Z G , et al . Condensable gases capture with ionic liquids [J ] . Chemical Reviews , 2023 , 123( 16 ) 10258 - 10301 .

Jiang Y F , Lei Z G , Yu G Q . Unraveling weak interactions between fluorinated gases and ionic liquids [J ] . Chemical Engineering Science , 2021 , 244 : 116792 .

Li H , Zhou P , Zhang J , et al . A theoretical guide for screening ionic liquid extractants applied in the separation of a binary alcohol-ester azeotrope through a DFT method [J ] . Journal of Molecular Liquids , 2018 , 251 : 51 - 60 .

Zhou M J , Zhang Y L , Xue K , et al . Separation of fuel additives based on mechanism analysis and thermodynamic phase behavior [J ] . Chinese Journal of Chemical Engineering , 2023 , 64 : 168 - 176 .

Doherty M F , Malone M F . Conceptual Design of Distillation Systems [M ] . New York : McGraw-Hill , 2001 .

Smith R . Chemical Process Design [M ] . New York : McGraw-Hill , 1995 .

Xiang S G , Wang L L , Wang Y L , et al . Exploration of gradient energy-saving separation processes for ethylene glycol mixtures based on energy, exergy, environment, and economic analyses [J ] . Separation and Purification Technology , 2021 , 279 : 119787 .

Wang L L , Huang X Y , Babaei M , et al . Full-scale utilization of geothermal energy: a high-efficiency CO 2 hybrid cogeneration system with low-temperature waste heat [J ] . Journal of Cleaner Production , 2023 , 403 : 136866 .

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