Separation of ethyl acetate–isooctane mixture by heteroazeotropic batch distillation

This paper studies the separation of an ethyl acetate–isooctane mixture by heterogeneous azeotropic distillation in a batch rectifying column. An initial list of 60 candidates was studied but only methanol and acetonitrile were obtained as potential heterogeneous entrainers. These entrainers form a low boiling heterogeneous azeotrope with isooctane. Experimental verification of the miscibility gap with isooctane was performed at 25 °C for each entrainer giving a smaller region for methanol than for acetonitrile. Feasibility of the heterogeneous azeotropic batch distillation was carried out experimentally in a laboratory batch distillation column having 44 theoretical equilibrium stages and using a high reflux ratio. Several distillate fractions were taken as a function of the temperature at the top of the column. For both methanol and acetonitrile, the main fraction was defined by the condensed vapor providing a liquid–liquid split of the isooctane/entrainer heteroazeotrope into the decanter. Ethyl acetate impurity was detected in both decanted phases, but in much lower amount when using acetonitrile as entrainer. The process with acetonitrile also resulted in a shorter operating time and higher purity and recovery yield of isooctane as the main distillate product. Pure ethyl acetate remained into the boiler at the end of each process.     

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.     

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。     

Feasibility of heterogeneous batch distillation processes

Synthesis of heterogeneous batch distillation is discussed, which aims at splitting azeotropic mixtures by adding an entrainer partially miscible with one of the initial binary mixture components. Key operational parameters are identified such as the amount of entrainer added in the ternary feed, the reflux policy, and the vapor line position by examples. Synthesis and operation are less straightforward for heterogeneous batch distillation than those for the homogeneous case, but offer many advantages: more design alternatives, simplified distillation sequences, a lower consumption of entrainer, and a crossing of distillation boundaries by the still path. Feasibility is assessed using simplified modeling and confirmed using a commercial batch process simulator package. Synthesis expectations and simulated results are verified throughout bench-plant experiments for the separation of the acetonitrile—water mixture using acrylonitrile as a light heterogeneous entrainer.     

Energy-Efficient Process with a Decanter to Separate Toluene-Methanol-Water Ternary Azeotropic Mixtures

An extractive distillation process with two columns and a decanter was proposed to separate ternary toluene-methanol-water azeotropic mixtures in a previous study. Based on this process, six processes were established to explore further energy-efficient schemes to separate the ternary azeotropic system. The optimal parameters of the process were determined in terms of the minimum total annual cost (TAC). The processes with heat integration perform better than those with a side stream or thermal coupling in terms of energy savings and TAC reduction. A process in which both the feed stream of the extractive distillation column and the entrainer recovery column are preheated by the entrainer recycle stream can reduce energy consumption by up to 27.69 % and TAC by 21.36 %.     

Design and control of acetic acid dehydration system via heterogeneous azeotropic distillation

Acetic acid dehydration is an important operation in the production of aromatic acid, such as terephthalic acid or in the manufacture of cellulose acetate. Although acetic acid and water does not form azeotrope, but using simple distillation to separate these two components is not practical. The reason is because the system has tangent pinch on the pure water end, thus it is more customary in industry to use an entrainer via a heterogeneous azeotropic distillation column system for the separation. In this study, a suitable entrainer is selected from three candidate acetates through rigorous steady-state simulation of this system. Optimum process design and operating condition are determined to keep high-purity bottom acetic acid composition and also keep a small acetic acid loss through top aqueous draw. Furthermore, the overall control strategy of this column system is proposed to hold both bottom and top product specifications in spite of feed rate and feed composition load disturbances. The proposed overall control strategy is very simple requiring only one tray temperature control loop inside the heterogeneous azeotropic column.     

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.     

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     

Operation and control of batch extractive distillation for the separation of mixtures with minimum-boiling azeotrope

Batch distillation is commonly used in the fine chemicals, specialty polymer, biochemical, pharmaceutical, and food industries. For separating mixtures with minimum-boiling azeotrope, a heavy entrainer is frequently added to the top section of the batch column to aid in the separation. This process is called batch extractive distillation. Most of the papers in open literature have only studied the first operating step of the batch extractive distillation which is the recovery of the light component without mentioning the later steps for the recovery of the other component and entrainer. In this paper, two real chemical systems, one separating acetone and methanol using water as entrainer and the other separating isopropyl alcohol (IPA) and water using dimethyl sulfoxide (DMSO) as entrainer, are studied for the feasible operation of the complete batch distillation sequence. The operating variables, including the pre-load amount with the mixture, continuous feed rate of the entrainer, and reflux ratio at each operating step are determined in the operating sequence. The constant reflux ratio and constant entrainer feed rate operating policy and another policy to allow these two operating variables to be varied will be compared in order to further improve the batch operation. All dynamic simulations that are performed directly mimic industrial situations from an empty column using a rigorous dynamic simulator, Aspen Dynamics™.     

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.     

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。     

Synthesis,experiments and simulation of heterogeneous batch distillation processes

The presence of azeotropes in multicomponent mixtures complicates the design of batch distillation separation processes widely used in pharmaceutical and speciality chemical industries. Most of those processes include the use of a homogeneous entrainer to ease the separation. We describe novel methods to break azeotropes using an entrainer that is partially miscible with one of the initial binary mixture components. We depict some of the advantages of heterogeneous batch distillation processes: more design alternatives for the separation of an azeotropic binary mixture than with homogeneous batch distillation, batch distillation boundary crossing thanks to a controlled reflux of the entrainer-rich phase, simplified distillation sequences as a consequence of less distillation tasks. Three examples based on the separation of non-ideal azeotropic or close boiling point binary mixtures through heterogeneous batch distillation are simulated using a commercial batch distillation package. Experiments validate the simulated separation of a minimum boiling azeotropic mixture.     

常规间歇萃取精馏分离苯-环己烷的研究

通过一个常规间歇萃取精馏实验装置,考察了不同萃取剂在不同回流比及萃取溶剂加入速率情况下对分离苯-环己烷共沸体系的影响。结果表明,二元混合溶剂能够解决单一溶剂的选择性与溶解性相矛盾的问题;且在同等条件下,综合性能优于单一溶剂;随着溶剂加入速率和操作回流比的增加,产品的产量逐渐提高,尤其重要的是混合溶剂间歇萃取精馏技术与简单溶剂间歇萃取精馏技术相比并不复杂。     

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.     

单乙醇胺(MEA)间歇萃取精馏甲醇-丙酮研究

用常规的间歇萃取精馏实验装置,研究了以单乙醇胺(MEA)为萃取剂间歇萃取精馏分离甲醇—丙酮恒沸物的过程。考察了萃取剂、全回流时间、共沸物组成、溶剂与混合物的体积比、回流比等因素对萃取精馏分离甲醇—丙酮共沸体系的影响,从而得出最优的萃取条件。     

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.     

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。     

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%。     

连续萃取催化精馏制备高纯度甲缩醛

研究了以甲醇和甲醛为原料,大孔径阳离子交换树脂为催化剂,通过将萃取精馏和催化精馏相耦合的方法制备高纯度甲缩醛,证明了这种工艺的可行性。在内径为35 mm、高为2700 mm的玻璃反应精馏塔内进行实验,考察了总进料量、萃取剂进料位置、醇醛摩尔比、回流比以及用甲醛溶液作为萃取剂对甲醛转化率和甲缩醛纯度的影响。在选定的实验条件下,甲醛的转化率可达到97.82%以上,甲缩醛纯度可达到97.64%（含甲醛0.79%、水1.41%、甲醇0.20%）。     

Comparison of extractive distillation and pressure-swing distillation for acetone/chloroform separation

The separation of acetone from chloroform is difficult because the highly nonideal vapor–liquid equilibrium produces a maximum-boiling azeotrope. An earlier paper (Luyben, W. L. (2008). Control of the maximum-boiling acetone/chloroform azeotropic distillation system. Industrial & Engineering Chemistry Research, 47, 6140–6149) discussed the use of extractive distillation for making this separation. This paper studies the use of pressure-swing distillation for making the same separation.Results show that the extractive distillation process is much more attractive from the standpoint of both capital investment and energy consumption. But pressure-swing distillation avoids the potential problem of product contamination by the extractive solvent that must be added to the binary system.