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.     

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.     

Flowsheet synthesis and complex distillation column design for separating ternary heterogeneous azeotropic mixtures

The boundary value method for design of distillation columns separating ternary heterogeneous azeotropic mixtures is extended to include complex configurations, i.e. columns with integrated decanters and with multiple heterogeneous stages; double-feed columns; columns with intermediate decanters. The methods can be used for establishing product feasibility in a column and evaluating a column design in terms of cost. Multiple feasible designs can be generated for a given set of product specifications, according to the reflux ratio, number of heterogeneous stages and liquid phase ratio; these designs may be evaluated with respect to operating and equipment costs. Case studies illustrate the design method.An algorithmic approach is presented for synthesising novel sequences for separating, by distillation and decanting, ternary heterogeneous azeotropic mixtures. Existing synthesis procedures that consider only simple single-feed columns with decanters and integrated decanters are extended to include more industrially relevant options such as columns with several heterogeneous stages, double-feed columns, columns with intermediate decanters, and those accepting a heterogeneous liquid feed. With these advanced column configurations included in the synthesis method, a wider range of sequences may be considered systematically, allowing sequences that are more economically attractive than conventional designs to be identified. A case study illustrates the approach.     

Process optimization of an industrial acetic acid dehydration progress via heterogeneous azeotropic distillation

The simulated process model of the HAc dehydration process under actual overloaded condition was conducted by amending the model of standard condition in our previous work using the process data collected from actual production. Based on the actual process model, the operation optimization analysis of each plant(HAc dehydration column, decanter and NPA recycle column) was conducted using Residue Curve Maps(RCMs),sensitivity analysis and software optimization module. Based on the optimized parameters, the influence of feed impurity MA and the temperature of decanter on the separating effect and energy consumption of the whole process were analyzed. Then the whole process operation optimizing strategy was proposed with the objective that the total reboiler duty Q Total of C-1 and C-3 reaches the minimum value, keeping C-1 and C-3 at their optimized separation parameters obtained above, connecting all the broken recycle and connection streams, and using the temperature of D-1 as operation variable. The optimization result shows that the total reboiler duty Q Total of the whole process can reach the minimum value of 128.32 × 10~6 k J·h~(-1) when the temperature of decanter is 352.35 K, and it can save 5.94 × 10~6 k J·h~(-1), about 2.56 t·h~(-1) low-pressure saturated vapor.     

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。     

乙二醇独乙醚-甲基异丁基酮-水三元非均相共沸物系分离过程

通过塔釜剩余曲线图、蒸馏边界线、液-液相平衡线等曲线,对乙二醇独乙醚-甲基异丁基酮-水三元非均相共沸物系进行理论分析,确定该物系分离需要共沸精馏、冷凝分相、油相部分回流、重组分回收、轻组分回收等5步工艺.通过流程设计、模拟计算、实验验证等研究,得到质量分数为99.24％甲基异丁基酮,质量分数为99.17％的乙二醇独乙醚...     

Conceptual design of an extractive distillation process for the separation of azeotropic mixture of n-butanol-isobutanol-water

In many chemical processes, large amounts of wastewater containing butanol and isobutanol are produced. Given that n-butanol-isobutanol-water can form triple azeotrope, high-purity butanol cannot be recovered from the wastewater by ordinary distillation. To economically and effectively recover butanol from this kind of wastewater, 1,4-butanediol is selected as an extractant to break the formation of the azeotropes, and a doubleeffect extractive distillation process is proposed. The conceptual design of the proposed process is accomplished based on process simulation. With the proposed process, the purity of recovered butanol and water is greater than 99.99 wt%. In comparison with the conventional azeotropic distillation process, economic analysis shows that the operating cost of the proposed process is lower:when the capacity of wastewater treatment is 100 t·h^-1, the total operating cost decreases by 5.385×10⁶ USD per year, and the total annual cost of the new process decreases by 5.249×10⁶ USD per year. In addition, in the extractive distillation system, variable effects on separation purities and cost are more complex than those in the ordinary distillation system. The method and steps to optimize the key variables of the extractive distillation system are also discussed in this paper and can provide reference for similar studies.     

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。     

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.     

醋酸-对二甲苯-水体系共沸精馏的模拟分析

采用Aspen Plus11.1化工流程模拟软件,对扬子石油化工有限公司化工厂精对苯二甲酸(PTA)装置的溶剂脱水塔生产过程进行了模拟计算,采用NRTL-HOC热力学计算模型,并进行热力学参数修正,通过调整塔板数、热负荷、进料位置、操作压力、对二甲苯(PX)采出位置等操作参数,得出各塔的最佳工艺条件。在最佳工艺条件下,分析了此分离过程的能耗问题。模拟结果表明,溶剂脱水塔分离得到的醋酸、水、PX均能达到产品质量要求,工艺流程合理、可靠。     

隔板塔共沸精馏分离二氯甲烷-乙腈-水-硅醚体系

以二氯甲烷-乙腈-水-硅醚为分离体系,采用自制隔板塔小试装置,研究了共沸剂回流比和液相分配比等操作参数对隔板塔分离效果的影响。实验结果表明,当气相分配比R_v为0.5,共沸剂回流比为3时,液相分配比R_l在[0.12,0.2]范围内,隔板塔分离效果较好。在实验的基础上,采用Aspen Plus软件对隔板塔共沸精馏工艺进行模拟,考察了隔板塔共沸精馏工艺最佳操作区域及节能效果。模拟结果表明,特定分离要求下,隔板塔存在一个使再沸器热负荷最小的最佳操作区域,在此最佳操作区域内,R_l和R_v相互关联,呈一一对应关系;与三塔串联简单精馏工艺相比,完成相同的分离任务,隔板塔共沸精馏工艺再沸器节能32.74%,冷凝器热负荷减少33.70%,乙腈回收率由66.47%提高到96.01%,且大幅降低设备投资。     

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.     

共沸精馏提纯丁醇的工艺优化研究及其工程应用

结合实践经验和工艺原理,利用丁醇和水组成的部分互溶系统的共沸特性,对从青霉素类结晶母液中提纯丁醇的生产工艺进行了分析研究,从设备布局、碱洗、废液处理和分水滞后等方面进行了优化处理。工程应用表明：与原工艺相比,优化工艺取得了良好的经济和能源效益,对从水相中共沸精馏提纯丁醇的生产有一定的实际参考价值。     

乙酸-水-乙酸正丁酯三相体系的热力学分析与共沸精馏过程模拟

乙酸-水-乙酸正丁酯体系的分离是汽-液-液三相共沸精馏过程,相分裂的判断和精馏塔算法的改进是进行该精馏过程模拟的两个主要问题.本文根据现有的基础数据给出了该体系的逸度和活度因子计算模型,然后讨论了Gibbs自由能的变化规律和热力学稳定性条件,给出了该体系相分裂判据,并得到了完整的相分裂区;最后,根据多相精馏的特点对现有的精馏塔算法进行了改进,对该三元非均相共沸精馏过程进行了数值模拟,所得沿塔温度和各组分浓度分布曲线与工业实测数据吻合.     

异丙醇-水间歇共沸精馏模拟研究

运用两点隐含法求解间歇共沸精馏过程平衡级恒摩尔持液模型的非线性刚性方程组。以异丙醇-水-环己烷为例进行模拟计算,并将模拟计算结果同实验结果相比较。结果表明,当共沸剂塔顶回流的回流比为1∶5时,分离得到的异丙醇浓度可以达到99.5%(质量分数);异丙醇的收率最高,最大收率可达78%;模拟计算结果与实验结果吻合得较好,模拟计算可以反映实际过程。     

Efficient optimization-based design for the separation of heterogeneous azeotropic mixtures

Model-based design of separation processes for heterogeneous azeotropic mixtures is a challenging task. The multiplicity of the solutions of equilibrium calculations and the discontinuity due to the potential switching between homogeneous and heterogeneous mixtures on a tray severely complicate the application of deterministic optimization. This paper presents a novel computational approach to reliably determine phase stability and the correct equilibrium solutions in every iteration of the optimization. The approach builds on the decomposition of the optimization problem into a generic superstructure model and an implicit model for equilibrium and enthalpy calculations, which is integrated into the optimization problem by means of an external function. The phase states and equilibrium solutions are determined by means of a reliable homotopy continuation algorithm. An additional reformulation of equilibrium solutions and enthalpy calculations allows overcoming the discontinuity problems. Different case studies illustrate the applicability and show the potential of the proposed method.     

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.     

萃取精馏分离异丙醇-水共沸体系的模拟与优化

对异丙醇-水共沸体系的萃取精馏过程进行模拟与优化。以乙二醇为萃取剂,基于UNIFAC模型,使用Aspen Plus化工模拟软件中的RadFrac模块进行萃取精馏模拟,并利用灵敏度分析模块对各工艺参数进行灵敏度分析与优化。结果表明,以乙二醇做萃取剂分离异丙醇-水共沸体系是可行的。对于处理流量5000kg·h-1的异丙醇-水共沸溶液,精馏塔具有22块塔板时,原料进料位置在第16块塔板,萃取液进料位置在第3块塔板,摩尔回流比为1.4,萃取剂与原料的进料比为2∶1,塔顶异丙醇质量分数可达0.9981,萃取精馏塔的分离效果和热负荷达到最优。模拟和优化的结果对工业化设计和生产具备指导意义。     

A framework for synthesizing the optimal separation process of azeotropic mixtures

In this work, a systematic framework is introduced to synthesize the optimal separation process of azeotropic mixtures. The proposed framework, which can handle an arbitrary number of components, consists of two main steps: a system analysis and a state‐space superstructure algorithm. The system analysis is composed of some equation‐oriented algorithms to supply basic information for the superstructure, including structure of the composition space, existence of unchangeable points and candidate operations. It is shown that the proposed superstructure featuring multistream mixing is superior to previous ones because it significantly expands the feasible area. Moreover, detailed design parameters such as number of stages and reflux ratio are derived. Additionally, flowsheet feasibility test rules are constructed to facilitate the analysis of the process, and are able to be used as heuristic methods to guide the design of ternary or quaternary systems. Three industrial cases are presented to illustrate the proposed framework. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

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.