两两共沸型均相三元物系萃取精馏中的定量构效模型与控制策略

项目来源

国家自然科学基金(NSFC)

项目主持人

王英龙

项目受资助机构

青岛科技大学

项目编号

21776145

立项年度

2017

立项时间

未公开

项目级别

国家级

研究期限

未知 / 未知

受资助金额

64.00万元

学科

化学科学-化学工程与工业化学-介科学与智能化工

学科代码

B-B08-B0806

基金类别

面上项目

关键词

构建模型建模 ; 萃取精馏 ; 剩余曲线 ; 动态特性 ; 流程模拟 ; extractive distillation ; residue curve ; modeling ; process simulation ; process dynamics

参与者

杨晶巍;陶少辉;李鑫;王永坤;赵永滕;赵婷然;贾慧;李敏;许希彩

参与机构

青岛科技大学

项目标书摘要:共沸物系的节能高效分离在过程工业中具有重要的科学意义与实用价值,萃取精馏已在二元共沸物分离上获得广泛应用。因精馏边界复杂、交互作用机理不明等原因,三元或多元共沸物分离的研究与应用较为迫切且颇具挑战性。项目选取两两共沸型均相三元共沸物,基于汽液相平衡实验结果利用分子模拟软件平台建立相对挥发度与微介观分子结构信息之间的定量构效关系模型,表征剩余曲线曲率特性并考察其与萃取精馏稳态工艺参数之间的相关联系,利用过程模拟软件从经济性与动态特性两方面对萃取精馏工艺流程进行多目标优化,阐明动态控制结构设计的规律,为实现两两共沸型均相三元混合物的萃取精馏过程提供策略与依据。项目注重利用基础实验、理论计算和模拟研究去揭示影响萃取精馏体系相对挥发度的本质因素,深入认识存在于萃取精馏中的微介观分子结构与宏观挥发性质及工艺参数的规律,对开拓三元共沸物系萃取精馏分离过程综合具有重要意义。

Application Abstract: The energy-saving and efficient separation of azeotropic mixtures is of important scientific and practical significance in the process industry.Extraction distillation has been widely used in the binary azeotrope separation.The research and application of the separation for ternary or multiple azeotropes are more urgent and challenging because of the complexity of the distillation boundary and the unclear interaction mechanism.The objectives of the project focus on ternary homogeneous systems with three binary azeotropes.Based on the results of vapor-liquid phase equilibrium experiments,the quantitative structure-activity relationship model between relative volatility and micro-mesoscopic molecular structure information will be established based on molecular simulation software platform,the curvature feature of residue curves will be characterized,and its correlation with steady-state process parameters of extractive distillation will be investigated.Multi-objective optimization of extractive distillation process will be performed using process simulation software from two aspects of economy and dynamic characteristics,and the rule of dynamic control structure design will be explained.The strategies and rules can be used to realize the process of extractive distillation for separating the homogeneous ternary systems with three binary azeotropes.The project focuses on revealing the essential factors which impact the relative volatility of extractive distillation system by basic experiments,theoretical calculations and simulation studies.Also,the rules existed among the micro-mesoscopic molecular structure,macroscopic relative volatility and the parameters of extractive distillation can be discovered.It is significant for exploring the synthesis of extractive distillation process with ternary azeotrope system.

项目受资助省

山东省

项目结题报告(全文)

共沸物系的节能高效分离在过程工业中具有重要的科学意义与实用价值,萃取精馏已在二元共沸物分离上获得广泛应用。因精馏边界复杂、交互作用机理不明等原因,多元共沸物分离的研究与应用较为迫切且颇具挑战性。本项目测定了30多组含低碳醇类、烷酯类等共沸物的400多组数据点,基于NRTL、UNIQUAC、Wilson模型关联得到了80多组二元交互作用参数;将分子动力学模拟、量子化学应用于萃取剂筛选与机理分析,从分子水平探究了萃取剂与共沸物分子的相互作用,萃取剂与共沸物之间的氢键强弱与萃取效果具有一致性,氢键的产生主要由萃取剂中氧原子上的一对孤电子控制,并通过模拟结果与实验数据相结合对比验证溶剂筛选的准确性,为萃取剂的筛选提供了理论依据;基于多目标优化得到同时兼顾经济与环境的最优操作参数工艺,通过热集成、热耦合等节能技术对萃取精馏进行强化,年度总成本可降低9.3-51%;分析回流比、温度等变量确定工艺的控制点,进而开发出工艺的最优控制策略,兼顾经济性与动态特性对萃取精馏工艺进行双目标优化;阐明动态控制结构设计与经济性之间的规律,对于低碳醇共沸物的分离工艺,动态控制难度随经济性的升高而增大,为实现三元两两共沸物的萃取精馏过程提供策略与依据。本项目通过将基础实验、理论计算和过程模拟研究相结合,从热力学相行为、分子作用机理两方面分析萃取剂与共沸混合物之间的构效关系,深入认识存在于萃取精馏中的微介观分子结构与宏观特性及工艺参数的规律,针对不同的三元共沸体系设计合适的工艺方案与控制策略,对三元两两共沸物系的分离具有重要指导意义。

  • 排序方式:
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  • 1.Progress and Challenges in the Electrocatalytic Reduction of Nitrate to Ammonia.

    • 关键词:
    • catalyst design strategies; electrocatalytic nitrate reduction mechanism; nitrate
    • Yin, Shupeng;Wang, Yinglong
    • 《Molecules 》
    • 2025年
    • 30卷
    • 19期
    • 期刊

    The escalating problem of nitrate pollution, coupled with the environmental burden of the Haber-Bosch process, has spurred intense interest in the electrocatalytic nitrate reduction reaction (eNO3RR) as a sustainable route for simultaneous wastewater treatment and ammonia production. However, the efficiency and selectivity of eNO3RR are hampered by the multi-step proton-coupled electron transfer process and the competing hydrogen evolution reaction. This review provides a comprehensive and critical overview of recent advances in understanding and designing catalysts for eNO3RR. We begin by elucidating the fundamental mechanisms and key reaction pathways, followed by a discussion on how critical parameters (e.g., electrolyte microenvironment, applied potential, reactor design) dictate performance. Further discussion of recent advances in catalysts, including single-metal catalysts, alloy catalysts, transition metal compounds, single-atom catalysts, carbon-based non-metal catalysts, and composite catalysts, highlights their significant roles in enhancing both the efficiency and selectivity. A distinctive feature of this review is its consistent critical assessment of catalysts through the dual lenses of practicality and sustainable development. Finally, we outline prevailing challenges and propose future research directions aimed at developing scalable and commercially viable electrocatalytic systems for green nitrogen management.

    ...
  • 2.Thermodynamic and economic analysis of a hydrogen production process from medical waste by plasma gasification

    • 关键词:
    • Biomass;Calorific value;Carbon;Economic analysis;Exergy;Hydrogen production;Ionic liquids;Synthesis gas;Waste treatment;Carbon conversion rate;Economics analysis;Exergy efficiencies;Higher heating value;Hydrogen product;Hydrogen production process;Medical wastes;Overall process;Plasma gasification;Thermo dynamic analysis
    • Yin, Kexin;Zhang, Runqi;Yan, Min;Sun, Lei;Ma, Yixin;Cui, Peizhe;Zhu, Zhaoyou;Wang, Yinglong
    • 《Process Safety and Environmental Protection》
    • 2023年
    • 178卷
    • 期刊

    To reduce the environmental pollution caused by pathogens and radioactive substances carried by medical waste, and alleviate the shortage of non-renewable energy, this work proposes a novel overall process for hydrogen production from medical waste by plasma gasification coupled with ionic liquid-based CO2 capture. The validity of the model is verified by the experimental data. Based on the simulation results, the effects of medical waste types, different gasification agents and carbon conversion rate on the syngas compositions, H2/CO ratio, carbon conversion rate, higher heating value and exergy efficiency are explored. The results show that the rate of hydrogen production from surgical masks is more than twice that of the other two types of medical waste. Steam is the best gasification agent. At this time, the higher heating value of syngas is 26.72 MJ/kg and the exergy efficiency is 78.25%. A comprehensive analysis of the thermodynamic efficiency and technical economy of the overall process shows that the total exergy efficiency is 70.84%. The production cost is 2115.74 USD and the raw material consumption is 2.61 t/t H2. This study can provide a promising theoretical guidance for the resource treatment of medical waste. © 2023 The Institution of Chemical Engineers

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  • 3.Economy, environmental assessment and energy conservation for separation of isopropanol/diisopropyl ether/water multi-azeotropes via extractive distillation coupled pervaporation process

    • 关键词:
    • Life cycle assessment; Extractive distillation coupled; pervaporation;Isopropanol; diisopropyl ether; water; azeotropes; Thermodynamicefficiency; Human toxicity;PRESSURE-SWING DISTILLATION; ISOPROPYL-ALCOHOL; ETHYLENE-GLYCOL;MEMBRANES; ETHANOL; DEHYDRATION; MIXTURE; WATER; OPTIMIZATION;COMBUSTION
    • Xu, Qinggang;Dai, Yasen;Zhao, Qing;Chen, Zhengrun;Cui, Peizhe;Zhu, Zhaoyou;Wang, Yinglong;Gao, Jun;Ma, Yixin
    • 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》
    • 2023年
    • 54卷
    • 期刊

    This wok proposed the extraction distillation coupled pervaporation (ED+PV) technology process using two different solvents to separate isopropanol (IPA) and diisopropylether (DIPE) from DIPE/IPA/H2O tern-ary heterogeneous azeotropes in industrial wastewater from the synthesis of isopropanol in this study. Based on strict design specifications, simulation and sequential iteration methods are used for process design and optimization. Compared to the ethylene glycol (EG)-EG+H2O process and the 1,3-propanediol (PDO)-IPA+H2O process, the total annual cost (TAC) of the EG-IPA+H2O process decreased by 20.76% and 7.86% (PDO). Compared to the EG-EG+H2O process, the TAC of the PDO-IPA+H2O process reduced 14%, but the global warming potential (GWP) and human toxicity of the PDO-IPA+H2O process increased 11.3% and 4.07% respectively. Compared to the PDO-IPA+H2O process, the EG-IPA+H2O process saves 7.86% (TAC), 9.78% (GWP) and 9.85% (human toxicity). The ED+PV process with EG is superior to PDO in factors of TAC, energy consumption, human toxicity and environment. The EG-IPA+H2O process changed the separation order of the products of the multi-azeotropic system, reduced the cost and energy conservation of the system, and enhanced the environmental protection evaluation of the process, is the best process through life cycle assessment for analyzing the economy, energy conservation, environmen-tal assessment and human toxicity, designing cleaner products, controlling waste discharge, and promot-ing the chemical purification industry. This work provides a new process design and optimized separation ideas, will have a good guiding significance for the research and application separation of multi-azeotropic mixture with mixed solvents in organic wastewater from the cleaner chemical produc-tion, has been up to standard wastewater discharge process, and realized the development goal of carbon peak and carbon neutrality in the sustainable development of chemical clean industry. (c) 2022 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.

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  • 4.Molecular dynamics-assisted process design and multi-objective optimization for efficient production of N-butyl acetate by reactive-extractive distillation/pervaporation

    • 关键词:
    • Reactive distillation; Extractive distillation; Pervaporation; Moleculardynamics; Multi-objective optimization;METHYL ACETATE; DISTILLATION; PERVAPORATION; SEPARATION; METHANOL;ENERGY; ESTERIFICATION; EQUILIBRIUM; PARAMETERS; MEMBRANE
    • Zhao, Qing;Li, Yanan;Li, Chen;Yan, Min;Zhu, Zhaoyou;Cui, Peizhe;Qi, Jianguang;Wang, Yinglong;Wang, Chuanxing
    • 《SEPARATION AND PURIFICATION TECHNOLOGY》
    • 2022年
    • 296卷
    • 期刊

    At present, the market demand for methyl acetate (MEOAC) is small and there is the problem of overcapacity. As an important organic solvent, n-butyl acetate (nBuOAC) is widely used in industry. It is very important to explore the efficient transesterification synthesis and separation process of nBuOAC. In this work, the schemes of reactive-extractive distillation (RED), side-line reactive extractive distillation (SLRED) and reactive distillationpervaporation (RDPV) were proposed for the transesterification of MEOAC and n-butanol (nBuOH) to synthesize nBuOAC and methanol (MEOH). Firstly, according to the relative volatility of MEOAC and MEOH azeotrope systems, and the interaction energy and radial distribution function (RDF) were calculated by molecular dynamics (MD) to complete the screening of extractants. Then the process design is completed based on reaction kinetics, and the established processes with optimal operating conditions were obtained by the multi-objective particle swarm optimization algorithm. Finally, the total annual cost (TAC) and gas emissions are used to assess the economic efficiency and environment performance of these processes and the optimal process was obtained. The calculation results show that among the three proposed processes, the RDPV process performs best economically and environmentally. The TAC of RDPV is 8.17% lower than that of RED and 6.46% lower than that of SLRED. Meanwhile, the TAC of SLRED is 1.83% lower than that of RED. The gas emissions of RDPV is 23.13% lower than that of RED and 23.51% lower than that of SLRED, and there is little difference between RED and SLRED process.

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  • 5.Mechanism analysis of solvent selectivity and energy-saving optimization in vapor recompression-assisted extractive distillation for separation of binary azeotrope

    • 关键词:
    • Quantum;chemical;calculation;Vapor;liquid;equilibria;DISTILLATION;Energy;saving;SEPARATION
    • Xiaomin Qiu;Yuanyuan Shen;Zhengkun Hou;Qi Wang;Zhaoyou Zhu;Yinglong Wang;Jingwei Yang;Jun Gao
    • 《中国化学工程学报:英文版》
    • 2022年
    • 6期
    • 期刊

    Octane and p-xylene are common components in crude gasoline,so their separation process is very important in petroleum industry.The azeotrope and near azeotrope are often separated by extractive distillation in indust

    ...
  • 6.The mechanism explosion of separating binary azeotropic system with intermediate-boiling-point solvent based on vapor–liquid equilibrium experiment, quantum chemical calculation and molecular dynamics simulation

    • 关键词:
    • Molecular dynamics;Extraction;Chemical analysis;Liquids;Boiling point;Hydrogen bonds;Quantum chemistry;Solvents;Heptane;Butyl acetate;Distillation process;Entrainer;Extraction distillation;Interaction energies;Intermediate-boiling-point solvent;n-Heptanes;Solvent based;Vapor + liquid equilibria;Σ-profile
    • Zhang, Hongru;Huo, Bingjie;Sun, Mengya;Shan, Rongli;Cui, Peizhe;Yang, Jingwei;Wang, Yinglong;Zheng, Shiqing
    • 《Journal of Chemical Thermodynamics》
    • 2022年
    • 168卷
    • 期刊

    For the extraction distillation process, the choice of entrainer is very important. Usually, the boiling point of the entrainer is higher than that of any of the components to be separated, while the mechanism of separation of azeotropic system with intermediate-boiling-point solvent as entrainer is not common. Taking the azeotrope of n-heptane and isopentyl alcohol as an example, the intermediate-boiling-point solvent of butyl acetate was determined as the entrainer. The experimental data of vapor–liquid equilibrium for the two systems of n-heptane isoamyl alcohol and n-heptane butyl acetate were analyzed. After the thermodynamic consistency test, the binary interaction parameters of three models were obtained by correlating and regressing the experimental data. The possibility and mechanism of the extraction of azeotropic system by the intermediate-boiling-point solvent were analyzed from the aspects of σ-profile, interaction energy and charge density by the principle of quantum chemistry and molecular dynamics. The results showed that the tendency of hydrogen bond between the intermediate-boiling-point solvent and the azeotropic system was different: one component interacted with each other in the form of hydrogen bond, and the other had no hydrogen bond. The mechanism of the intermediate-boiling-point solvent as the entrainer to separate azeotropic system was verified in the extractive distillation process.
    © 2022 Elsevier Ltd

    ...
  • 7.The mechanism explosion of separating binary azeotropic system with intermediate-boiling-point solvent based on vapor–liquid equilibrium experiment, quantum chemical calculation and molecular dynamics simulation

    • 关键词:
    • Molecular dynamics;Extraction;Chemical analysis;Liquids;Boiling point;Hydrogen bonds;Quantum chemistry;Solvents;Heptane;Butyl acetate;Distillation process;Entrainer;Extraction distillation;Interaction energies;Intermediate-boiling-point solvent;n-Heptanes;Solvent based;Vapor + liquid equilibria;Σ-profile
    • Zhang, Hongru;Huo, Bingjie;Sun, Mengya;Shan, Rongli;Cui, Peizhe;Yang, Jingwei;Wang, Yinglong;Zheng, Shiqing
    • 《Journal of Chemical Thermodynamics》
    • 2022年
    • 168卷
    • 期刊

    For the extraction distillation process, the choice of entrainer is very important. Usually, the boiling point of the entrainer is higher than that of any of the components to be separated, while the mechanism of separation of azeotropic system with intermediate-boiling-point solvent as entrainer is not common. Taking the azeotrope of n-heptane and isopentyl alcohol as an example, the intermediate-boiling-point solvent of butyl acetate was determined as the entrainer. The experimental data of vapor–liquid equilibrium for the two systems of n-heptane isoamyl alcohol and n-heptane butyl acetate were analyzed. After the thermodynamic consistency test, the binary interaction parameters of three models were obtained by correlating and regressing the experimental data. The possibility and mechanism of the extraction of azeotropic system by the intermediate-boiling-point solvent were analyzed from the aspects of σ-profile, interaction energy and charge density by the principle of quantum chemistry and molecular dynamics. The results showed that the tendency of hydrogen bond between the intermediate-boiling-point solvent and the azeotropic system was different: one component interacted with each other in the form of hydrogen bond, and the other had no hydrogen bond. The mechanism of the intermediate-boiling-point solvent as the entrainer to separate azeotropic system was verified in the extractive distillation process. © 2022 Elsevier Ltd

    ...
  • 8.Separation of isopropyl ether and acetone using ionic liquids based on quantum chemistry calculation and liquid–liquid equilibrium

    • 关键词:
    • Bond length;Hydrogen bonds;Solvents;Quantum chemistry;Acetone;Ethers;Extraction;Hydrogen bond acceptors;Hydrogen bond donors;Isopropyl ethers;Liquid liquid equilibrium;Methylimidazole;Quantum chemical calculations;Quantum chemistry calculations;Quantum-chemical calculation;Sulphonates;Trifluoromethane
    • Zhang, Yanli;Li, Huiyuan;Li, Haixia;Shan, Rongli;Zhu, Zhaoyou;Wang, Yinglong;Gao, Jun
    • 《Journal of Chemical Thermodynamics》
    • 2022年
    • 167卷
    • 期刊

    Selecting green and efficient extractive solvents are the inevitable requirement of sustainable development. Ionic liquids as green solvents are widely used in the separation of organic substance. In this manuscript, ionic liquids are used as extractive solvents to separate isopropyl ether-acetone system. The selected ionic liquids are 1-ethyl-3-methylimidazole dinitrile amine [EMIM][DCA], n-butyl-3-methylimidazole trifluoromethane sulfonate [BMIM][OTF], 1-ethyl-3-methylimidazole trifluoromethane sulfonate [EMIM][OTF]. Firstly, the relation between H-bonding donor and H-bonding acceptor is description by COSMO-SAC model based on the extraction mechanism. After that the experiments of liquid–liquid equilibrium are conducted at T = 298.15 K and P = 101.325 kPa, and the liquid–liquid equilibrium data are correlated by NRTL model. The results indicate that the model has a good correlation with the experimental results. Finally, the extraction mechanism is discussed at micro scale. The H-bonding interaction between ionic liquids and acetone, including total charge density, bond length, deformation charge density and interaction energy, is determined by quantum chemistry calculation. The quantum chemical calculation and experimental process provide theoretical guidance for the highly efficient separation of acetone - isopropyl ether binary system.
    © 2021 Elsevier Ltd

    ...
  • 9.Economic effect of an efficient and environmentally friendly extractive distillation/pervaporation process on the separation of ternary azeotropes with different compositions

    • 关键词:
    • Extractive distillation; Pervaporation; Feed composition; Sequentialiterative optimization algorithms; Economic effect;PERVAPORATION MEMBRANE BIOREACTOR; WASTE-WATER TREATMENT; DISTILLATION;DESIGN; OPTIMIZATION; DEHYDRATION; ADSORPTION; ADSORBENT; REMOVAL; LAYER
    • Zhang, Hongru;Zhao, Qing;Zhou, Mengjin;Cui, Peizhe;Wang, Yinglong;Zheng, Shiqing;Zhu, Zhaoyou;Gao, Jun
    • 《JOURNAL OF CLEANER PRODUCTION》
    • 2022年
    • 346卷
    • 期刊

    Exploring the process of cost-effective and efficient technology to separate ternary aqueous azeotropic systems has become essential research in chemistry and materials science. Traditional distillation technology and promising membrane technology occupy an irreplaceable position in wastewater treatment. However, single separation technology for the separation of azeotropic systems has disadvantages. To better meet the industrial practical needs of different azeotropic compositions in each process of rapeseed oil production, the separation performance and economic cost of single extractive distillation and an extractive distillation coupled pervaporation process for ternary azeotropic systems with different feed compositions were studied. Environmentally friendly and effective solvents were selected as extractants in the extractive distillation process from two aspects: selectivity and biological toxicity. Sequential iterative optimization algorithms were used to optimize the process with the ratio of water to the total amount of cyclohexane and isopropanol ranging from 1:9 to 9:1, considering cost as the evaluation index. The results showed that the cost of the processes increases significantly with increasing water content in the feed composition. Because the flux and selectivity of the membrane module were considerably affected by temperature when the water content was less than 0.4, the integrated process was more economical; otherwise, the extractive distillation process was more economical when the water content was greater than 0.4.

    ...
  • 10.Process design and optimization of the efficient production of butyl acrylate by reactive azeotropic distillation/pervaporation using different feed ratios

    • 关键词:
    • Reaction; Distillation; Pervaporation; Environment; Azeotropic;DISTILLATION-PERVAPORATION; ACETATE PRODUCTION; HYBRID PROCESS; DIVIDINGWALL; SEPARATION; MEMBRANE; ENERGY; CARBONATE; COLUMN; POLYMERIZATION
    • Zhao, Qing;Shen, Yuanyuan;Li, Yanan;Zhu, Zhaoyou;Cui, Peizhe;Gao, Jun;Ma, Yixin;Wang, Yinglong;Wang, Chuanxing
    • 《JOURNAL OF CLEANER PRODUCTION》
    • 2022年
    • 344卷
    • 期刊

    Present industrial development has a great demand for butyl acrylate, an important basic chemical. Efficient synthesis and separation processes are very important for the clean manufacturing of butyl acrylate. In this work, two processes for the preparation of butyl acrylate by reactive distillation coupled with azeotropic distillation (RD-AD) or pervaporation (RD-PV) were proposed. By changing the ratio of reactants, the economic performance of the two processes under different specifications of butyl acrylate was analyzed, and the environmental impact of the two processes in the production process were analyzed. First, the process design using different purity specifications was completed focusing on the reaction kinetics. Then, based on the sequential iterative algorithm, process optimization was carried out with the minimum total annual cost (TAC) as the objective function, and the process with optimal operating conditions was obtained. Finally, TAC and the global warming potential (GWP), acidification potential (AP), abiotic depletion potential (ADP) and human toxic potential (HTP) were used to assess the economic and environmental performance of the proposed processes. The results showed that the RD AD process had better economic performance, whereas the RD-PV process had better environmental performance. According to the results, the parameters that influenced the TAC for products with different purities were obtained. The TAC of the RD-AD process was 41.39% lower than that of the RD-PV process, and GWP, AP, and ADP of the RD-PV process were respectively 12.67%, 13.68%, and 13.07% lower than those of the RD-AD process.

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