萃取精馏分离苯/环己烷共沸体系模拟与优化

以糠醛作为萃取剂分别使用常规萃取精馏、隔壁塔萃取精馏和差压热集成萃取精馏对苯和环己烷体系进行分离研究,使用流程模拟软件Aspen Plus V8.4进行模拟分析,对初步设计的三稳态流程,分别进行灵敏度分析,使用多目标遗传算法对过程进行整体优化以获得最优结构参数。结果表明,隔壁塔萃取精馏和差压热集成萃取精馏相对于常规萃取精馏所需再沸器热负荷可分别减小21.5%和15.7%。对三工艺流程进行经济性分析,发现与常规流程相比,隔壁塔萃取精馏的年总费用下降了6.0%,而差压热集成萃取精馏年总费用增加了50.8%,为萃取精馏分离苯/环己烷共沸体系工业化设计提供了理论依据和设计参考。     

Heterogeneous extractive batch distillation of chloroform-methanol-water: Feasibility and experiments

A novel heterogeneous extractive distillation process is considered for separating the azeotropic mixture chloroform-methanol in a batch rectifying column, including for the first time an experimental validation of the process. Heterogeneous heavy entrainer water is selected inducing an unstable ternary heteroazeotrope and a saddle binary heteroazeotrope with chloroform (ternary diagram class 2.1-2b). Unlike the well-known heterogeneous azeotropic distillation process and thanks to continuous water feeding at the column top, the saddle binary heteroazeotrope chloroform-water is obtained at the column top, condensed and further split into the liquid-liquid decanter where the chloroform-rich phase is drawn as distillate. First, feasibility analysis is carried out by using a simplified differential model in the extractive section for determining the proper range of the entrainer flowrate and the reflux ratio. The operating conditions and reflux policy are validated by rigorous simulation with ProSim Batch Column^® where technical features of a bench scale distillation column have been described. Six reproducible experiments are run in the bench scale column matching the simulated operating conditions with two sequentially increasing reflux ratio values. Simulation and experiments agree well. With an average molar purity higher than 99%, more than 85% of recovery yield was obtained for chloroform and methanol.     

Separation of ethylene glycol, 1,2-butanediol and 1,2-propanediol with azeotropic distillation

1,2-butanediol (1,2-BDO) and 1,2-propanediol (1,2-PDO) are inevitably side produced in the ethylene glycol (EG) production processes from non-petroleum routes, but are very difficult to separate by the ordinary distillation method because of the closeness of their boiling temperatures to EG, thus compromise the economy of these processes. The azeotropic distillation process using 1-octanol (CPO) as an entrainer to separate EG and 1,2-BDO mixture with or without 1,2-PDO was studied in this paper. Four binary vapour–liquid equilibrium data of EG-1,2-BDO, EG-CPO, 1,2-BDO-CPO, and 1,2-PDO-CPO were measured using an Ellis equilibrium kettle and regressed with the thermodynamic model of non-random two liquid to obtain the corresponding binary interaction parameters. On this basis, azeotropic distillations with CPO as an entrainer were designed to separate EG and 1,2-BDO with or without 1,2-PDO. The complete separation processes, including the azeotropic distillation and CPO recovery process consisting of extraction with H₂O and subsequent distillation, were simulated and optimized with Aspen Plus for both the EG-1,2-BDO binary mixture and the EG-1,2-BDO-1,2-PDO ternary mixture. The simulation results show that the azeotropic distillation method with CPO as an entrainer can effectively separate the mixture of EG-1,2-BDO and EG-1,2-BDO-1,2-PDO, achieving EG of 99.90% purity with 99.98% recovery and 1,2-BDO of 99.30% purity with 99.45% recovery for the binary mixture, and achieving EG of 99.90% purity with 99.80% recovery, 1,2-BDO of 99.35% purity with 99.35% recovery, and 1,2-PDO of 90.59% purity with 94.38% recovery for the ternary mixture. These processes are promising for industrial application and can significantly improve the economy of non-petroleum EG production.     

乙醇脱水塔内两相和三相共沸精馏

研究了乙醇脱水塔内的两相共沸精馏和汽液液三相共沸精馏过程。利用Aspen plus模拟软件对乙醇脱水塔内4种工况的精馏曲线、共沸剂浓度分布、回流量和再沸器能耗进行了分析比较。结果表明,苯做共沸剂时,脱水塔内两相共沸精馏和汽液液三相共沸精馏的精馏曲线、共沸剂浓度分布、回流量和再沸器能耗相近,脱水塔精馏曲线都跨越了精馏边界,并且共沸剂在塔内大多数板上都有较高浓度分布。而环己烷做共沸剂时,两相共沸精馏工况和汽液液三相共沸精馏工况条件下的脱水塔内精馏曲线、共沸剂浓度分布、回流量和再沸器能耗有较大差别。汽液液三相共沸精馏工况条件下,环己烷在塔内大多数板上有较高浓度分布,起到较好的脱水作用,而两相共沸精馏工况条件下脱水塔内共沸剂仅分布在塔顶几块塔板上,塔内多数板上没有起到共沸剂作用。     

Systematic design of an extractive distillation for maximum‐boiling azeotropes with heavy entrainers

Extractive distillation is one of the most attractive approaches for separating azeotropic mixtures. Few contributions have been reported to design an extractive distillation for separating maximum‐boiling azeotropes and no systematic approaches for entrainer screening have been presented. A systematic approach to design of two‐column extractive distillation for separating azeotropes with heavy entrainers has been proposed. A thermodynamic feasibility analysis for azeotropes with potential heavy entrainers was first conducted. Then, five important properties are selected for entrainer evaluation. Fuzzy logic and develop membership functions to calculate attribute values of selected properties have been used. An overall indicator for entrainer evaluation is proposed and a ranking list is generated. Finally, the top five entrainers from the ranking list have been selected and use process optimization techniques to further evaluate selected entrainers and generate an optimal design. The capability of the proposed method is illustrated using the separation of acetone–chloroform azeotropes with five potential entrainers. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3898–3910, 2015     

甲醇-丙酮共沸物分离的研究进展

主要介绍了甲醇-丙酮共沸物系变压精馏和萃取精馏两种分离方法的研究进展。经过比较,萃取精馏方法在经济成本方面更具有显著优势。关于萃取精馏,首先阐述了萃取剂的选取以及近些年来萃取剂的研究,主要集中在3个方面:传统单一溶剂、各种盐类和离子液体。其次还介绍了各种萃取剂所对应的气液平衡模型的应用情况和操作条件的优化等方面,并对萃取精馏及其萃取剂的应用提出了展望。     

Separation of tert‐Butyl Alcohol‐Water Mixtures by a Heterogeneous Azeotropic Batch Distillation Process

Tert‐butyl alcohol and water form an azeotrope at normal pressure. Simple distillation cannot be used to separate these two components. In this article, a systematic study of the separation of tert‐butyl alcohol–water mixtures with an entrainer by heterogeneous azeotropic batch distillation was performed. Based upon the thermodynamic behavior of the ternary mixtures, cyclohexane was chosen as the entrainer. It formed ternary and binary heterogeneous azeotropes with the original components. The process feasibility analysis was validated by using rigorous simulation with chemical process simulation software – HYSYS Plant 2.2 and DISTIL 4.1. Simulation results were then corroborated in a batch experimental column for the selected entrainer.     

共沸精馏分离乙醇-异丙醇

为了分离乙醇-异丙醇混合物,研究了共沸精馏在乙醇-异丙醇物系中的应用。根据共沸剂的选取原则选定出1-己烯作为共沸精馏分离乙醇-异丙醇混合物的共沸剂,使用ASPEN模拟软件模拟连续和间歇共沸精馏分离乙醇-异丙醇工艺流程,并通过间歇共沸精馏实验考察了所选共沸剂的分离效果。结果表明：使用1-己烯作为共沸剂能成功的分离乙醇-异丙醇混合物;采用有30块理论板的填料塔,回流比为25,共沸剂1-己烯与乙醇的质量比为4∶1,塔釜异丙醇的质量分数达到99.77%。     

Energy-efficient recovery of tetrahydrofuran and ethyl acetate by triple-column extractive distillation:entrainer design and process optimization

An energy-efficient triple-column extractive distillation process is developed for recovering tetrahydrofuran and ethyl acetate from industrial effluent.The process development follows a rigorous hierarchical design procedure that involves entrainer design,thermodynamic analysis,process design and optimization,and heat integration.The computer-aided molecular design method is firstly used to find promising entrainer candidates and the best one is determined via rigorous thermodynamic analysis.Subsequently,the direct and indirect triple-column extractive distillation processes are proposed in the conceptual design step.These two extractive distillation processes are then optimized by employing an improved genetic algorithm.Finally,heat integration is performed to further reduce the process energy consumption.The results indicate that the indirect extractive distillation process with heat integration shows the highest performance in terms of the process economics.     

Separation of aqueous isopropanol by reactive extractive distillation

A new separation method of reactive extractive distillation is proposed for the separation of isopropanol and water, using the mixture of ethylene glycol (C₂H₆O₂) and glycollic potassium (C₂H₅O₂K) as an entrainer. Vapor–liquid‐equilibrium (VLE) measurements confirmed that the entrainer was effective for this separation. Using a feed/solvent volume ratio of 1:1, isopropanol with a concentration over 96.0% weight fraction was obtained by the reactive extractive distillation process and the azeotropic point was eliminated. A novel process of separating isopropanol and water is designed on the basis of reactive extractive distillation to obtain the product with different concentrations, which may have a lasting value in industry. © 2002 Society of Chemical Industry     

Design and control of extractive distillation for the separation of methyl acetate-methanol-water

The azeotrope of methyl acetate methanol and water was isolated using extractive distillation with water as entrainer. The pressure-swing extractive distillation (PSED) process and vapor side-stream distillation column (VSDC) with the rectifier process were designed to separate the methyl acetate, methanol and water mixture. It was revealed that the VSDC with the rectifier process had a reduction in energy consumption than the PSED process. Four control schemes of the two process were investigated: Double temperature control scheme (CS1), Q_R/F feedforward control of reboiler duty scheme for PESD (CS2), Q_R/F feedback control scheme for VSDC (CS3), the feedback control scheme of sensitive plate temperature of side-drawing distillation column to dominate the compressor shaft speed (CS4). Feed flow and composition disturbance were used to evaluate the dynamic performance. As a result, CS4 is a preferable choice for separation of methyl acetate-methanol-water mixture. A control scheme combining the operating parameters of dynamic equipment with the control indicators of static equipment was proposed in this paper. It means using the sensitive plate temperature of side-drawing column to control the compressor shaft speed. This is a new control scheme for extractive distillation.     

Process intensification on the separation of benzene and thiophene by extractive distillation

The separation of benzene and trace thiophene by extractive distillation was intensified in two aspects, that is, selection of a suitable entrainer and improvement of the process. The mixture of dimethylformamide (DMF) and an ionic liquid (IL) was chosen as the entrainer. Vapor–liquid equilibrium (VLE) experiments using pure DMF and a mixed entrainer were conducted, and UNIFAC model for ILs was extended to the benzene‐thiophene‐DMF‐IL system. The results demonstrated that volatilization loss of DMF in the vapor phase was significantly reduced by adding IL. Moreover, an improved process with only four columns using a mixed entrainer was proposed. The results indicated that the improved process is more promising for decreasing energy consumption and equipment investment compared with the conventional six‐column process. The total heat duties of reboilers and condensers was decreased by 6.47% and 6.41%, respectively. The process intensification strategy may be directly extended to separate trace components of other systems. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4470–4480, 2015     

Comparison of continuous homogenous azeotropic and pressure-swing distillation for a minimum azeotropic system ethyl acetate/n-hexane separation

Continuous homogenous azeotropic distillation (CHAD) and pressure-swing distillation (PSD) are explored to separate a minimum-boiling azeotropic system of ethyl acetate and n-hexane. The CHAD process with acetone as the entrainer and the PSD process with the pressures of 0.1 MPa and 0.6 MPa in two columns are designed and simulated by Aspen Plus. The operating conditions of the two processes are optimized via a sequential modular approach to obtain the minimum total annual cost (TAC). The computational results show that the partially heat integrated pressure-swing distillation (HIPSD) has reduced in the energy cost and TAC by 40.79% and 35.94%, respectively, than the conventional PSD, and has more greatly reduced the energy cost and TAC by 62.61% and 49.26% respectively compared with the CHAD process. The comparison of CHAD process and partially HIPSD process illustrates that the partially HIPSD has more advantages in averting the product pollution, energy saving, and economy.     

Economic evaluation of energy saving alternatives in extractive distillation process

Until now, there has not been consensus about the superiority of thermally coupled sequence over the conventional sequence in the extractive distillation process. In this sense, the main goal of this paper is to analyze three approaches for saving energy in the extractive distillation process: optimization, thermal integration and thermal coupling. Three azeotropic mixtures were investigated: ethanol and water (M1); tetrahydrofuran and water (M2); and acetone and methanol (M3). The solvents were ethylene glycol for M1 and M2, and water for M3. The results are shown in terms of the total annual cost (TAC) and specific energy consumption (SEC), and revealed that a thermally coupled extractive distillation sequence with a side rectifier did not always present the best results. Taking the case studies from literature as a starting point (without thermal integration), the optimization procedure used in this work found that TACs are always lower. The inclusion of thermal integration in configurations led to reducing TAC for all mixtures under investigation when compared to the sequences without this integration. When comparing two modifications in the layout of extractive distillation, it can be seen that it is more advantageous to use the preheating of the azeotropic feed with the recycle stream from the recovery column of the conventional sequence than using a thermally coupled sequence.     

醋酸甲酯和甲醇热集成变压精馏分离工艺模拟与优化

基于对醋酸甲酯与甲醇二元共沸特性的分析,提出热集成变压精馏分离醋酸甲酯和甲醇的工艺. 利用Aspen Plus软件对该分离过程进行模拟,以NRTL活度系数方程为物性计算方法,其二元相互作用参数由气液相平衡数据回归,分析了加压塔和常压塔的理论板数、进料位置及回流比对分离效果的影响,并进行了能耗比较. 结果表明,该工艺能很好地分离醋酸甲酯和甲醇,较佳的工艺条件为：加压塔操作压力909 kPa,理论板数32,第21块板进料,回流比4.2,塔釜醋酸甲酯纯度99.8%;常压塔操作压力101 kPa,理论板数30,第20块板进料,回流比4.6,塔釜甲醇纯度99.0%. 与常规变压精馏相比,热集成变压精馏可节能达45.8%;与以水为萃取剂的萃取精馏分离工艺相比,热集成变压精馏分离工艺更适合醋酸甲酯与甲醇体系的分离.     

Isobaric vapor-liquid equilibrium for methanol+benzene+1-octyl-3-methylimidazolium tetrafluoroborate

Isobaric vapor-liquid equilibrium (VLE) data for {methanol (1)+benzene (2)+1-octyl-3-methylimidazolium tetrafluoroborate (3)} where 3 is an ionic liquid ([OMIM]⁺[BF₄]^?) at atmospheric pressure (101.32 kPa) were measured with a modified Othmer still. The results showed that the ionic liquid studied can transfer the azeotropic point and eliminate the azeotropic phenomena when its concentration is up to x₃=0.30. This means that [OMIM]⁺[BF₄]^? can be used as a promising entrainer in the application of extractive distillation. The measured ternary data were correlated using the NRTL model.     

Feasible separations and entrainer selection rules for heteroazeotropic batch distillation

A feasibility analysis is presented for the separation of close-boiling and azeotropic (minimum- and maximum-boiling) binary mixtures into pure components by the addition of an entrainer introducing a heterogeneous azeotrope. The analysis is done for both the conventional batch rectifier and the multivessel batch column. The analysis is theoretical and based on the assumptions of total reflux/reboil ratios and infinite number of stages. Two feasibility conditions are formulated that make it possible to investigate feasibility based on information coming solely from the distillation line map along with the binodal curve of the ternary mixture. Serafimov's classification is used for classifying the azeotropic phase diagrams. The feasibility analysis provides the necessary background and information for formulating rules for entrainer selection for the process. Two simple rules are then proposed, which make it possible to “screen” entrainers for heteroazeotropic batch distillation with minimum efforts.     

A reactive distillation process with a sidedraw stream to enhance the production of isopropyl acetate

This paper designs an entrainer combined with a sidedraw to enhance the reactive distillation (RD) process of isopropyl acetate (IPAc). Acetic acid (HAc) reacts with isopropanol (IPOH) to generate IPAc and water (H₂O). The ratio of IPAc to H₂O in the products of esterification is smaller than that in the minimum boiling IPAc–IPOH–H₂O azeotrope, resulting in a mass of organic phase reflux to remove the surplus H₂O from the top of the RD column. This process consumes a high amount of energy. For better energy efficiency, a feasible design flowsheet includes an RD column, a stripper, a top decanter, a middle decanter, and a sidedraw stream to intensify the azeotropic separation where an entrainer is introduced to carry out the surplus water from the middle of the RD column in the form of a liquid phase. The key design variables in the proposed flowsheet are determined to obtain a minimal total annual cost (TAC). As a result, an optimal process design is drawn out while satisfying the stringent specifications for product purity. These results show that the energy requirements of the IPAc system can be decreased by 27.55%.     

Heat Integrated Ethanol Dehydration Flowsheets

Abstract

A theoretical evaluation of heat-integrated heterogeneous-azeotropic ethanol-water distillation flowsheets is presented. Simulations of two column flowsheets using several different hydrocarbon entrainers reveal a region of potential heat integration and substantial reduction in operating energy. In this paper, methods for comparing hydrocarbon entrainers are shown.

Two aspects of entrainers are related to operating and capital costs. The binary azeotropic composition of the entrainer-ethanol mixture is related to the energy requirements of the flowsheet. A temperature difference in the azeotropic column is related to the size of the column and overall process staging requirements. Although the hydrophobicity of an entrainer is essential for specification of staging in the dehydration column, no substantial increase in operating energy results from an entrainer that has a higher water content. Likewise, liquid-liquid equilibria between several entrainer-ethanol-water mixtures have no substantial effect on either staging or operation. Rather, increasing the alcohol content of the entrainer-ethanol azeotrope limits its recovery in the dehydration column, and increases the recycle and reflux streams. These effects both contribute to increasing the separation energy requirements and reducing the region of potential heat integration.

A cost comparison with a multieffect extractive distillation flowsheet reveals that the costs are comparable; however, the extractive distillation flowsheet is more cost effective as operating costs increase.

The destruction of organic model substances by indirect electrooxidation was investigated. The oxidation agent Co(III) was used because of the high redox potential of the Co(III)/Co(II) redox couple (E₀ = 1.808 V).

Several supercritical fluid extraction (SCFE) processes have been proposed for removing toxic and intractable organic compounds from a range of contaminated solids. These include soil remediation and the regeneration of adsorbents used to treat wastewater streams such as granular activated carbon (GAC). As a separation technique for environmental control, SCFE has several distinct advantages over conventional liquid extraction methods and incineration. Most notably, the contaminant is removed from the solvent in a concentrated form via a change in pressure or temperature and can be completely separated upon expansion to atmospheric pressure.

The viability of SCFE hinges on process conditions such as solvent-feed ratio and solvent recycle ratio. The necessity of recycling solvent complicates the contaminant separation step since a complete reduction to atmospheric pressure would create large recompression costs. Because of this, the pressure and temperature dependence of contaminant solubility must be understood so that operating conditions for the separation step can be defined. Fortunately, this is the most developed aspect of SCF technology. However, the mass transfer limitations to removing contaminants from solids change with solvent flow rate.

This paper discusses the use of SCFE for environmental control and presents results for the removal of DDT and 2-chlorophenol from GAC. 2-chlorophenol is almost completely removed with pure CO₂ at 40°C and 101 bar while only 55% of the DDT is removed at 40°C and 200 bar. These differences in regeneration efficiency cannot be understood solely in terms of solubility but point to a need for detailed studies of adsorption equilibrium and mass transfer resistances in supercritical fluid systems.     

Design and Control of Extraction Distillation for Dehydration of Tetrahydrofuran

Design and control of an extractive distillation system for tetrahydrofuran (THF) dehydration with ethylene glycol as entrainer is investigated. The main module is a two‐column system containing an extractive distillation column, whose top stream is the desired product THF, and an entrainer recovery column. Economic analysis with total annual cost as the objective function is developed. Two kinds of control strategies are explored for THF dehydration. The responses reveal that the control structure with fixed reflux ratio cannot maintain the bottom liquid level of the entrainer recovery column, while the control scheme with fixed reboiler heat duty/feed flow ratio exhibits good control performance in spite of large deviations in feed flow rate and feed composition.