Choice of suitable entrainer in heteroazeotropic batch distillation system for acetic acid dehydration

Mixture containing acetic acid and water does not form azeotrope. However, because of tangent pinch on the pure water end, it is customary in industry to add an entrainer into this mixture to aid the separation via heterogeneous azeotropic distillation. When the production scale is relatively small, it is more beneficial to run the acetic acid dehydration in batch mode. In Chien et al. [Chien, I. L., K. L. Zeng, H. Y. Chao, and J. H. Liu, “Design and Control of Acetic Acid Dehydration System via Heterogeneous Azeotropic Distillation,” Chemical Engineering Science, 59, 4547 (2004)], a suitable entrainer for acetic acid dehydration operating in continuous mode was found to be iso-butyl acetate. This paper demonstrates that although iso-butyl acetate is a good entrainer for continuous heterogeneous azeotropic distillation system, it is not suitable in heteroazeotropic batch system for acetic acid dehydration. Instead, the performances of two other acetates are compared for the suggestion of better entrainer in batch operation. An extremely simple batch operating sequence for acetic acid dehydration will be demonstrated via dynamic simulation. The proposed batch operation is very robust in terms of the particular values chosen for the operating variables. This proposed batch operation gives very similar separation performance comparing to a multivessel operation and requires less process, instrumentation, and control equipments.     

非均相共沸精馏研究进展

非均相共沸精馏广泛应用于共沸物和近沸物的分离。文章介绍了非均相连续共沸精馏和非均相间歇共沸精馏关键技术的研究进展。对共沸精馏中的关键问题如共沸剂的选择做了详细论述和验证。利用残余曲线法对非均相共沸精馏的过程可行性进行了分析和讨论。     

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.     

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.     

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.     

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™.     

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.     

非均相共沸间歇精馏模拟

提出了非均相共沸间歇精馏过程计算模型。将共沸精馏塔分为再沸器，塔体，冷凝器和液相分层器几部分，用Newton-Raphson法与泡点法结合对这4个部分进行迭代计算。经实例模拟表明，操作条件指定合理，本模型只需要用很简单的初值，能以较快的速度收敛到正确解。本模型对间歇精馏操作具有一定的指导作用。     

Design and Control of Heterogeneous Azeotropic Distillation for Separating 2‐Methylpyridine/Water

In industrial processes, 2‐methylpyridine/water mixtures can be separated via the conventional heterogeneous azeotropic distillation (HAD) using benzene as entrainer. 2‐Methylpyridine and water can form a heterogeneous azeotrope by themselves, based on which an improved HAD process is proposed. This allows for reducing the total operating cost and total annual cost (TAC) by more than one‐tenth compared with the conventional HAD process. Two different control structures were established for the enhanced HAD process. The results indicate that applying the feedforward ratio controllers to the control structure can handle the feed disturbances and maintain product purities with smaller transient deviations and shorter settling times.     

New double column system for heteroazeotropic batch distillation

A new double column system (DCS) operated in closed mode is suggested for heterogeneous batch distillation. This configuration is investigated by feasibility studies based on the assumption of maximal separation and is compared with the traditional batch rectifier (BR). We study the configurations also by dynamic simulation based on a detailed model using a professional simulator. For the new configuration the minimal duration of the process is determined. The influence of the most important operational parameters is studied. The calculations and the simulations are performed for a binary (n-butanol–water) and for a ternary heteroazeotropic mixture (isopropanol–water + benzene as entrainer). One of the advantages of the DCS is that distillation of binary and ternary systems is performed in only one step. Furthermore the recovery of components is usually higher and the amount of byproducts is lower.     

Batch‐Rektifikation azeotroper Gemische in Verstärkungs‐ und Abtriebskolonnen

Batch distillation is an efficient unit operation which allows the separation of a multicomponent mixture into its pure constituents in a single column. However, the separation of azeotropic mixtures by distillation is quite difficult because at the azeotrope the liquid and the gas have the same composition and, in turn, the driving force for distillation disappears. A systematic presentation of batch distillation processes for the separation of binary azeotropic mixtures using an entrainer is given.     

加盐萃取-精馏耦合分离苯-环己烷共沸物

采用N,N-二甲基甲酰胺(DMF)+硫氰酸钾(KSCN)萃取分离苯-环己烷共沸物,并用常规间歇精馏处理富含苯的萃取液。考察了不同溶剂与原料液的体积比、盐质量分数对该体系分配系数及选择系数的影响,并进行了多级错、逆流萃取实验及精馏实验。实验结果表明:7级错流萃取可得摩尔分数大于97%(脱溶剂摩尔分数)的环己烷;5级逆流可得摩尔分数大于75%(脱溶剂摩尔分数)的环己烷;精馏后的萃取液,苯摩尔分数可达98%以上,DMF+KSCN摩尔分数可达96%以上。加盐萃取-精馏耦合分离苯-环己烷共沸物可得到令人满意的分离效果,是一种绿色节能的新方法。     

合成氨工艺正丙醇废液精馏处理的工艺技术

采用共沸精馏技术处理合成氨工艺流程中脱碳工段产生的含大量正丙醇混醇废液。本文采用共沸精馏的方法,选用合理可行的共沸剂,在间歇精馏塔内进行正丙醇-水共沸物系的分离实验,优化了该共沸精馏技术处理工业混醇废液的最佳操作条件。结果表明：采用共沸精馏方法,以环己烷为共沸剂,可使原料液中20%～40%的正丙醇含量提纯至质量分数≥95%,塔顶回收的共沸剂质量分数≥97%。该工艺流程较大地减小了设备投资和能耗。实验表明采用共沸精馏技术用于正丙醇-水共沸物系的分离具有可靠性和实用性。     

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.     

Influence of entrainer recycle for batch heteroazeotropic distillation

Dehydration of isopropanol applying batch heteroazeotropic distillation with toluene as entrainer (E) is investigated. The composition of the feed is near to that of the isopropanol (A)-water (B) azeotrope. The effects of recycling the entrainer and the off-cut are studied by dynamic simulation with a professional flow-sheet simulator. Three consecutive batches (one production cycle) is studied. Both operational modes (Mode I: decantation after distillation and Mode II: decantation during distillation) are simulated. For Mode II, calculations are performed both for Strategy A (distillate from the aqueous (E-lean) phase only) and Strategy B (partial withdrawal of the organic (Erich phase), as well). The E-rich phase, the final column hold-up and the off-cut (Mode II only) are recycled to the next batch. The influence of the following parameters are determined: quantity of entrainer, reflux ratios of the steps. The variations caused by the recycling in the 2^nd and 3^rd batches are also shown. The best results (lowest specific energy demand and highest recovery of A) are obtained by Mode II, Strategy A. Recycling increases the recovery, and drastically diminishes the entrainer consumption. However, it makes the production slower and decreases the quantity of fresh feed that can be processed.

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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.     

共沸蒸馏在化工生产中的应用与研究进展

共沸蒸馏为共沸物或相对挥发度接近于1的非理想物系的分离过程提供了选择。介绍了蒸馏残余曲线图的热力学原理,并以反应蒸馏生产乙酸乙酯工艺为例说明了蒸馏残余曲线图在流程设计等方面的应用。分别从夹带剂选择、过程设计、过程集成强化、过程控制等角度阐述了共沸蒸馏过程相关理论研究进展;在应用方面,主要综述了乙醇、异丙醇稀溶液、稀乙酸等脱水及回收利用情况,共沸蒸馏过程强化反应蒸馏、变压共沸蒸馏、共沸蒸馏耦合膜分离研究进展情况以及反应蒸馏工艺的局限性,并对其未来的发展前景作了展望。     

间歇共沸精馏分离乙醇一水体系的改进研究

间歇共沸精馏是分离共沸物的一种方法,适用于化工、制药、溶剂回收、天然产物提取等产量小、品种多的行业,因此间歇共沸精馏近年来已成为非常活跃的研究和开发热点.对已有的常规间歇共沸精馏的操作方式作了改进,即共沸剂改为在塔釜回流,以正己烷为共沸剂,对分离乙醇-水共沸体系进行了改进研究,并与常规间歇共沸精馏的实验结果进行比较.结...     

Feasibility studies for batch extractive distillation with a light entrainer

Our former method for the assessment of the feasibility of batch extractive distillation (usually performed in a rectifier with a heavy entrainer) was extended to the case where a light entrainer is fed continuously into a rectifier or a stripper. The method is based on the calculation of the vessel path and possible composition profiles of the column sections. The method is demonstrated for both configurations on the examples of separation of minimum boiling point azeotropic mixtures. For the rectifier the most important conclusions were also experimentally verified.     

Retrofit design of a pharmaceutical batch process considering “green chemistry and engineering” principles

Considering the capital intensive nature of the chemical industry, redesign of existing production plants is a strategic decision. In this study, retrofitting is performed using a systematic path flow decomposition method, enriching it with hazard assessment and life cycle analysis path flow indicators and proposing a classification scheme for coupling these new path flow indicators with relevant heuristics for process alternative generation. The developed methodology is applied in a batch production plant from the pharmaceutical industry. The method highlights solvent recovery or substitution as important retrofitting actions, generates diverse process layout structures to achieve this task and evaluates them from cost, hazard and life cycle assessment point of view. Extractive distillation using glycol as an entrainer is identified as the multiobjective optimal option for separating the THF/Water azeotrope with improvement up to 40% for the various objectives compared with a base case where the waste solvent is incinerated. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3423–3440, 2015