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。     

Optimization study on the azeotropic distillation process for isopropyl alcohol dehydration

Modeling and optimization work was performed using benzene as an entrainer to obtain a nearly pure anhydrous isopropyl alcohol product from dilute aqueous IPA mixture through an azeotropic distillation process. NRTL liquid activity coefficient model and PRO/II with PROVISION 6.01, a commercial process simulator, were used to simulate the overall azeotropic distillation process. We determined the total reboiler heat duties as an objective function and the concentration of IPA at concentrator top as a manipulated variable. As a result, 38.7 mole percent of IPA at concentrator top gave the optimum value that minimized the total reboiler heat duties of the three distillation columns.     

醋酸浓度对钛在共沸溶液中的腐蚀行为影响

钛盘的腐蚀是醋酸精馏塔安全稳定生产过程中亟待解决的一个问题,然而,影响钛材腐蚀的因素较多,很多腐蚀规律还不清楚。基于某化工厂钛材醋酸精馏塔的实际腐蚀工况,采用电化学阻抗谱和动电位极化法原位研究了钛材在不同模拟共沸醋酸溶液中的腐蚀行为,用金相显微镜观察了腐蚀前后的形貌变化,对极化曲线和阻抗谱曲线进行了模拟计算得到腐蚀动力学参数,探讨了腐蚀溶液浓度和腐蚀时间对钛板腐蚀行为的影响规律,分析了腐蚀机理,发现醋酸浓度和腐蚀时间对钛板的腐蚀影响较大,高浓度醋酸共沸体系中钛有利于钝化,当醋酸浓度由60％增大至97．5％时,钝化膜阻抗AK486．7Q增大至16000Q,腐蚀速率从5．80×10-10g／（m2-a）降低至5．66×10-11g／（m2．a）,但是腐蚀时间延长会破坏钝化膜,97．5％醋酸的共沸溶液中,当腐蚀时间由30min增大至60min时,钝化膜阻抗从16000Q降低至14600Q,腐蚀速率Ak5．66×10-11g／（m2．a）增大至2．97×10-10g／（m2．a）。实验结果为工业醋酸精馏塔中钛的防护提供了重要参考价值。     

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.     

The use of dilute acetic acid for butyl acetate production in a reactive distillation: Simulation and control studies

The recovery of dilute acetic acid, which is widely found as a by-product in many chemical and petrochemical industries, becomes an important issue due to economic and environmental awareness. In general, separation of acetic acid in aqueous solution by conventional distillation columns is difficult, requiring a column with many stages and high energy consumption. As a result, the primary concern of the present study is the application of reactive distillation as a potential alternative method to recover dilute acetic acid. The direct use of dilute acetic acid as reactant for esterification with butanol to produce butyl acetate in the reactive distillation is investigated. Simulation studies are performed in order to investigate effect of the concentration of dilute acetic acid and key process parameters on the performance of the reactive distillation in terms of acetic acid conversion and butyl acetate production. In addition, three alternative control strategies are studied for the closed loop control of the reactive distillation. The control objective is to maintain the butyl acetate in a bottom product stream at the desired purity of 99.5 wt%.     

丙酮-四氢呋喃-水混合物的清洁分离工艺的概念设计

引言 四氢呋喃（THF）既是一种性能优良的贵重有机溶剂,又是一种重要的有机合成中间体,因此在制药、涂料、皮革等领域应用广泛．当四氢呋喃用作溶剂时,由于其不被消耗,往往需要进行回收．但四氢呋喃易与水、丙酮等其他极性溶剂形成共沸物,而生产中又常需要四氢呋喃的纯度足够高,进而增加了分离提纯难度．     

糠醛废水中的醋酸回收工艺

使用自制络合萃取剂,采用脉冲填料塔通过络合萃取回收糠醛废水中的醋酸,萃取效率可达到97％～99％。测定了该物系的液液平衡数据,试验考察了影响萃取效率的因素。以醋酸的精制可利用减压精馏蒸出和共沸精馏脱水来实现。萃取液中醋酸蒸出率接近100％,脱水效果良好,得到合格的工业级醋酸。     

六甲基二硅烷-甲苯-水混合物的清洁分离工艺设计

在对六甲基二硅烷(HMDO)-甲苯-水三元体系进行了热力学分析的基础上,应用化工流程模拟软件ASPEN PULS对工艺过程进行模拟。提出了共沸蒸馏、萃取的分离方案,筛选了5种共沸剂,结果表明丙酮为最佳共沸剂。丙酮与HMDO-水形成共沸物,分离甲苯;共沸物通过萃取的方式分离HMDO;水与丙酮可以通过普通精馏的方法得以分离,整个过程中的共沸精馏溶剂和萃取剂-水全部循环使用,没有废液的排放,实现了清洁生产。提出的工艺方案可为工业装置设计提供参考。     

MINLP optimization of a heterogeneous azeotropic distillation process: Separation of ethanol and water with cyclohexane as an entrainer

Heterogeneous distillation processes are widely used in industry for the separation of azeotropic and close-boiling mixtures. This paper addresses the optimization of a heterogeneous distillation process for the separation of an azeotropic ethanol/water mixture using cyclohexane as an entrainer. Starting from a given process superstructure a MINLP problem is set up to consider continuous as well as discrete decision variables such as the feed locations and the number of stages of the distillation columns. A modified Generalized Benders Decomposition algorithm to account for non-convexities of the model equations solves the MINLP problem. The algorithm can be attached via Visual Basic for Applications (VBA) to any commercial process simulator with NLP and VBA capabilities. Various optimization runs show that the algorithm is easily applicable and returns solutions independent of the initial values.     

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.     

Untersuchung der batchweisen Azeotroprektifikation zur Trennung des Gemischs Essigsäure/Wasser

The aim of the present work is to investigate the suitability of the UNIFAC method to properly simulate the batch azeotropic distillation of a mixture of acetic acid, water, and ethyl acetate. A batch distillation including upstream countercurrent liquid‐liquid extraction was performed at pilot scale. A dedicated analytical method for fast and robust determination of top and bottom products was developed and presented. Experimental data were finally used for the validation of numerical predictions. It could be demonstrated that the UNIFAC method is applicable for the simulation of such a complex transient distillation process.     

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.     

Kinetics of acetic acid esterification over ion exchange catalysts

Computer simulation showed that catalytic distillation is an attractive process for the removal of dilute acetic acid from wastewater. Selection of catalysts and kinetic data have been obtained for the design of the catalytic distillation column. Kinetic measurements were conducted in a batch reactor. Methanol was added to the dilute acetic acid solutions and reacted with the acid in water to form methyl acetate and water. The reaction can be catalyzed by solid acid catalysts. It was found that Amberlyst 15 was an effective catalyst for this reaction. The effects of stirrer speed, reaction temperature, reactant concentration and catalyst loading on reaction rate were investigated. A complete kinetic equation for describing the reaction catalyzed by Amberlyst 15 was developed. This equation can be used in the simulation and design of the catalytic distillation column for removing acetic acid from wastewater.     

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.     

乙酸乙酯的精制方法

介绍了几种乙酸乙酯的精制方法,并分析了它们的优缺点。分别介绍了用乙酸和乙醇酯化反应合成乙酸乙酯,通常可采用传统的四塔连续工艺过程;添加促进剂萃取精制过程;加饱和盐水萃取脱水工艺过程;加有机溶剂萃取分离过程;加恒沸剂共沸蒸馏和乙酸萃取反应精馏过程。乙醛缩合法生产乙酸乙酯的三塔连续精馏过程以及乙烯与乙酸气相催化反应的加水精制工艺过程。     

磺酰氯生产废液中醋酸的回收利用

磺酰氯是生产除草剂噻吩磺隆的中间体,其生产过程中要使用大量醋酸作为溶剂,醋酸如果不回收,将全部作为废液排放,造成严重的污染和浪费。由于废液成分复杂,醋酸的回收利用比较困难。通过比较各方法优劣,分别采用恒沸精馏和溶剂萃取的方法进行了醋酸回收实验,结果表明,恒沸精馏难以达到预期目的,而溶剂萃取则可以实现醋酸的分离和循环利用,回收的醋酸经厂家实验证明完全符合生产要求。     

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 STRATEGY FOR ACETIC ACID RECOVERY

Acetic add is recovered from dilute aqueous solutions by extraction followed by azeotropic distillation. The heat required for distillation accounts for the major proportion of the cost of the process. Therefore, the proper selection of the entrainer is of great importance. In this paper, a procedure for preliminary entrainer selection is developed combining the well proved heuristic approaches and the latest developments for the synthesis phase based on residue curve maps and liquid-liquid equilibria plots. The energy requirements for the most promising entrainers are calculated using a commercial process simulator. It was found that methyl tert-butyl ether is a promising entrainer for the acetic acid dehydration process.