Investigating the need of a pre-concentrator column for acetic acid dehydration system via heterogeneous azeotropic distillation

In our previous study [Chien, I.L., Zeng, K.L., Chao, H.Y., Liu, J.H. (2004). Design and control of acetic acid dehydration system via heterogeneous azeotropic distillation. Chemical Engineering Science 59(21), 4547-4567.], an acetic acid dehydration system has been designed. The suitable entrainer selected for that system is iso-butyl acetate. Design and control of the system has been studied in detail to maintain high-purity bottom acetic acid concentration and also keep a small acetic acid loss through top aqueous draw. In that previous study, the feed composition is assumed to contain equal molar of acetic acid and water. However, in a typical waste acid recovery application, the above assumption may be too rich in acetic acid. In this paper, a feed stream containing 80 mol% water and 20 mol% of acetic acid is investigated. Several design alternatives can be deduced including one commonly used in industry by adding a pre-concentrator column in the upstream of a heterogeneous azeotropic distillation column. The necessity of this pre-concentrator column from design and control view points will be thoroughly investigated in this paper. The final recommended process design is a tradeoff between total annual cost (TAC) and operability of the system. The recommended design is a single heterogeneous azeotropic distillation column with aqueous reflux stream. Very wide feed composition and flow rate changes can be handled by this design with proper choice of the overall control strategy.     

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.     

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.     

工业PTA溶剂脱水过程动态模拟与分析

Dynamic model for dehydration process of industrial purified terephthalic acid solvent is investigated to understand and characterize the process.A temperature differential expression is presented,which ensures the equation to convergence and short computation time.The model is used to study the dynamic behavior of an azeotropic distillation column separating acetic acid and water using n-butyl acetate as the entrainer.Responses of the column to feed flow and aqueous reflux flow are simulated.The movement of temperature front is also simulated.The comparison between simulation and industrial values shows that the model and algorithm are effective.On the basis of simulation and analysis,control strategy,online optimization and so on can be implemented effectively in dehydration process of purified terephthalic acid solvent.     

工业醋酸脱水过程五元体系非均相共沸精馏的流程模拟

针对以醋酸正丙酯为共沸剂的醋酸脱水过程,考虑醋酸溶剂中未反应的前体对二甲苯以及反应的副产物醋酸甲酯的影响及回收利用,分别选用HOC和UNIQUAC模型来修正体系中五元混合物系的汽液非理想性,通过拟合醋酸甲酯-对二甲苯和醋酸正丙酯-对二甲苯两体系的二元汽液平衡实验数据获得了该两组体系UNIQUAC模型的二元交互作用参数,借助模拟软件Aspen Plus,结合软件内置其他二元体系参数,对工业醋酸脱水塔系包括溶剂脱水塔、PX回收塔、共沸剂回收塔在内的三塔体系进行系统的分析模拟,得到了与工艺数据误差小于±6%的能正确描述工业醋酸脱水塔系操作特性的工艺机理稳态模型,为工业醋酸脱水过程工艺的进一步研究提供理论基础和依据。     

Optimal design of mixed acid esterification and isopropanol dehydration systems via incorporation of dividing-wall columns

This study explores the design of a reactive distillation system and that of a heterogeneous azeotropic system by incorporating dividing-wall column (DWC). The first system involves the esterification of mixed acid (acetic acid and propionic acid) with methanol. Simulation studies are carried out for conventional reactive distillation sequence as well as for reactive dividing-wall distillation system. Both systems are optimized by an iterative optimization procedure. Optimal design results show that the reactive dividing-wall system saves steam consumption by 45.2% and reduces total annual costs (TAC) by 34.5%. The second case investigated is a heterogeneous azeotropic distillation system involving dehydration of crude isopropyl alcohol with cyclohexane as entrainer. Two optimal separation systems are generated, including one with a single-dividing wall column and one with a double-dividing wall column. In comparison with an energy-efficient azeotropic distillation sequence containing two stripping columns by Chang et al. (2012) [1], simulation results show that the former two systems can cut steam usage further by 6.0%. The two systems save about 5.4–6.1% in terms of TAC. DWCs prove to be superior to the convention distillation systems with respect to both cost and energy efficiency.     

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。     

Design of entrainer-enhanced reactive distillation for the synthesis of butyl cellosolve acetate

An innovative entrainer-enhanced reactive distillation (RD) process is presented, which aims to the production of high-purity butyl cellosolve acetate from butyl cellosolve and acetic acid via an esterification reaction. This entrainer-enhanced RD process can procure technical advantages from both heterogeneous azeotropic distillation and RD. Solvents such as cyclohexane, ethylene dichloride, toluene, and octane are considered as candidates in this esterification RD process. The function of entrainers is to simplify the separation between water and acetic acid. For this purpose, the proper entrainer to use is thus evaluated based on its mutual solubility with water in two liquid phases. Simulation results reveal that total annual cost can be substantially reduced when cyclohexane, toluene, and octane are used as entrainers in the RD column. The octane-enhanced RD provides the most economical design in this studied case.     

Energy saving in acetic acid process using an azeotropic distillation column with a side stripper

Dilute acetic acid is obtained primarily from fermentation and synthesis processes and cannot be produced by simple distillation due to relatively low volatility of acetic acid compared to water. Instead, an azeotropic distillation is applied to increase the concentration of dilute acetic acid. When acetic acid is extracted from a dilute aqueous solution using a solvent mixture of ester and alcohol, its recovery requires an energy-intensive azeotropic distillation. In the water stripping process that follows azeotropic distillation, two distillation columns handle the acetic acid and water mixture in similar composition. Therefore, the two columns can be combined as a side stripper connected to the azeotropic distillation column. The energy-saving effect is examined with the HYSYS (Aspentech Corporation) evaluation of the process. Compared to the conventional process, the modified process suggests 39% reduction in heating duty and 24% coolant savings. The economic analysis shows 32% decrease in investment and 36% utility savings. Based on heat utilization analysis, the thermodynamic efficiency is enhanced by 11%.     

结合图论和基团贡献法的非均相共沸精馏挟带剂设计

非均相共沸精馏挟带剂的计算机辅助分子设计(CAMD)由分子合成、分子筛选及分子确认3个环节递进构成。在分子合成环节,预选基团,限定合成分子的基团总数及类型,基于图论原理实现由基团到分子的自动合成。在分子筛选环节,依据基础物性筛选指标形成基础分子库,输入待分离物系,采用非均相共沸物形成判据筛选出若干候选分子。在分子确认环节,由非均相共沸温度及组成、挟带剂的汽化热等参数组成模糊综合评判函数,实现分子排序,从而输出一组较优挟带剂。以乙酸-水物系、乙腈-乙酸乙酯物系为例,得到了相应设计结果,与文献结果进行了对比。研究表明该方法及所编程序具备可靠实用性,可为近沸程及共沸混合物分离过程的开发与设计提供先导性支持。     

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.     

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。     

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。     

萃取、共沸精馏技术联用回收废液中的醋酸

针对化工生产过程中产生的稀醋酸溶液难以回收高纯度醋酸的问题,首先采用乙酸乙酯和苯的混合溶剂萃取浓缩稀醋酸溶液;再通过精馏蒸出溶液中的萃取剂和部分水;最后采用乙酸丁酯作为挟带剂,用共沸精馏法分离得到醋酸。得到的醋酸质量分数达96.84%,回收率达84.97%。对工业化回收稀醋酸溶液中的醋酸有一定的实用价值。     

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.     

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 %.     

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.     

间歇共沸精馏分离乙二醇单甲醚-水物系

通过绘制乙二醇单甲醚-水-共沸剂的简捷剩余曲线,提出了以乙酸异丙酯作为间歇共沸精馏法分离乙二醇单甲醚-水物系的共沸剂。然后完成剩余曲线数据的测定实验,根据实验数据绘制乙二醇单甲醚-水-乙酸异丙酯三元物系的剩余曲线图,确定了乙二醇单甲醚-水共沸物系的分离工艺。并通过实验研究了共沸剂加入量对乙二醇单甲醚回收率的影响,从而确定了适宜的共沸剂配比：当共沸剂与原料中水的质量比为2～2.5时,乙二醇单甲醚的一次性收率在90%以上。     

Computer control and computer aided operation of acetic acid recovery process

A computer system has been developed for a process to recover acetic acid from an aqueous solution. The process uses solvent extraction and series of distillation columns. The control system uses from periodic off-line process optimization to determine set points and othe parameters. Acid concentration in the feed stream drawn from an adjoining plant changes considerably. When such fluctuations occur, the computer has to keep the acidity of the raffinate at the pre-calculated optimal value. In the main distillation column, both bottom and top purity must be strictly controlled. Control logic in an on-line mini computer provides noninteracting cotrol of reflux reboiler steam in the column and feed-forward and feedback control for the solvent/feed ratio using sampled data.