Reactive pressure swing batch distillation by a new double column system

Ethyl-acetate is generally produced by the esterification reaction of ethanol with acetic-acid. Since the reaction is equilibrium-limited, the use of reactive distillation is an attractive option. A new double-column system is suggested for ethyl-acetate production by applying reactive pressure swing batch distillation. The system was investigated by a feasibility study based on the analysis of reactive and non-reactive residue curve maps. Two different process options were found to be feasible. In the first option, the reactive column operates at the lower pressure (1.01 bar), and the non-reactive column that removes ethyl-acetate from the system operates at the higher pressure (10 bar). The second option allows the reactive column to operate at the higher pressure (10 bar), and the non-reactive column removes water at the lower pressure (1.01 bar). The first process option was studied by rigorous simulation based on less simplifying assumptions using a professional dynamic simulator. The influence of the most important operation parameters was also studied.     

Feasibility of new pressure swing batch distillation methods

The pressure swing distillation in different batch column configurations is investigated by feasibility study and rigorous simulation calculations. Besides studying the well known batch configurations (rectifier, stripper, middle vessel column) we also suggest two novel configurations such as double column batch rectifier (DCBR) and double column batch stripper (DCBS). The alternate application of a batch rectifier and a batch stripper is also studied. The feasibility method is based on the assumption of maximal separation. The results of the feasibility studies are verified by rigorous simulations based on less simplifying assumptions. The calculations are made by a professional dynamic flow-sheet simulator for the separation of a minimum (ethanol–toluene) and a maximum boiling (water–ethylene-diamine) azeotropic mixture. The different column configurations are compared. The DCBS (for the separation of the minimum azeotrope) and the DCBR (for the maximum azeotrope) showed several advantages (e.g. only one production step without pressure change, lower energy consumption) compared with the other configurations.     

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.     

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.     

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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Dynamic composition estimation for a ternary batch distillation

A novel Kalman estimator has been proposed to provide the estimates of dynamic composition in a ternary batch distillation process operated in an optimal-reflux policy. The estimator is formulated based on a sequence of reduced-order process models representing a whole batch behavior. Therefore, the full-order models are first developed around different pseudo-steady-state operating conditions along batch optimal profiles. Then they reduce their orders to achieve all state observability and controllability by a balanced truncation method. In the estimator scheme, the reduced models as well as relevant covariance matrices of process noise are pre-scheduled and switched according to any desired periods. Four important issues have been studied including selection of a sensor frequency, effects of an integrating step size, a state initialization and a measurement noise. The performances of the reduced estimator have been investigated and compared with those of a conventional nonlinear estimator. Simulation results have demonstrated that the performances of the novel linear estimator are reasonably good and almost identical to the nonlinear estimator in all cases, though the linear estimator performs rather sensitively to the effect of high measurement noise. Nevertheless, it has been found to be applicable to implement in real plants with much lower computation effort, easier state initialization and unrequired a priori knowledge of thermodynamics.     

Cyclic total reflux batch distillation with two reflux drums

The present work proposes a novel cyclic total reflux (CTR) operation of batch distillation with two reflux drums working alternatively. A mathematical model is set up for the process. The computational comparison of the novel policy with the regular constant reflux and non-cyclic total reflux (NCTR) operations is also presented. The experimental runs of the new mode show that it can be operated and controlled more easily. The novel operation is significantly time saving compared to the mode of regular constant reflux theoretically and experimentally. The two reflux drum mode of CTR is also suitable for the separation of the mixture containing a large amount of light component.     

Dynamic parameter estimation and optimization for batch distillation

This work reviews a well-known methodology for batch distillation modeling, estimation, and optimization but adds a new case study with experimental validation. Use of nonlinear statistics and a sensitivity analysis provides valuable insight for model validation and optimization verification for batch columns. The application is a simple, batch column with a binary methanol–ethanol mixture. Dynamic parameter estimation with an ℓ₁-norm error, nonlinear confidence intervals, ranking of observable parameters, and efficient sensitivity analysis are used to refine the model and find the best parameter estimates for dynamic optimization implementation. The statistical and sensitivity analyses indicated there are only a subset of parameters that are observable. For the batch column, the optimized production rate increases by 14% while maintaining product purity requirements.     

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™.     

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.     

Composition estimation of multicomponent reactive batch distillation with optimal sensor configuration

An inferential state estimation scheme based on extended Kalman filter (EKF) with optimal selection of sensor locations using principal component analysis (PCA) is presented for composition estimation in multicomponent reactive batch distillation. The properties of PCA are exploited to provide the most sensitive dynamic temperature measurement information of the process to the estimator for accurate estimation of compositions. The state estimator is supported by a simplified dynamic model of reactive batch distillation that includes component balance equations together with thermodynamic relations and reaction kinetics. The performance of the proposed scheme is evaluated by applying it for composition estimation on all trays, reboiler, reflux drum and products of a reactive batch distillation column, in which ethyl acetate is produced through an esterification reaction between acetic acid and ethanol. This quaternary system with azeotropism is highly nonlinear and typically suited for implementation of the proposed scheme. The results demonstrate that the proposed EKF estimation scheme with optimal temperature sensor configuration is effective for inferential estimation of compositions in multicomponent reactive batch distillation.     

一个用于精馏塔模拟的新模型

A new computational mass transfer model is proposed for simulating the distillation process by solving the fluctuating mass flux for the closure of turbulent mass transfer equation in order to obtain the concentration profile and the separation efficiency of distillation column. The feather of the proposed model is to abandon the conventional way of introducing the turbulent mass transfer diffusivity (dispersion coefficient) to the turbulent mass transfer equation. To verify the validity of the proposed model, a commercial scale packed column and a sieve tray column were simulated and compared with published experimental data. The simulated results were satisfactorily confirmed in both concentration distribution and separation efficiency.     

间歇萃取精馏操作过程的实验研究

采用复合式精馏塔实现了萃取精馏的间歇操作,塔顶产品物质的量分数达95%以上。以取得合格产品的量与时间之比作为目标函数,研究了回流比R、中间回流量Vm(中间罐向提馏段进料流量)、萃取剂用量S对萃取精馏过程的影响,在R=5～10,Vm=3.2～7.2mL/min,S=1.2～2.2mL/min范围内,随以上操作参数的增大,目标函数均呈先增大后减小的趋势。     

基于双塔精馏的甲醇-碳酸二甲酯分离工艺

基于甲醇和碳酸二甲酯体系的共沸特性,应用双效热集成和分割式热泵两种双塔精馏工艺进行该体系的分离研究。利用文献报道的实验数据对选用的Wilson物性方程中的二元交互作用参数进行回归修正。利用Aspen Plus模拟软件,以年运行总费用最小为目标函数,分别对提出的两种双塔精馏工艺进行模拟与优化,得到合适的工艺参数。模拟结果表明,两种双塔精馏工艺均比单塔加压精馏工艺其能耗更低、年运行总费用更少。就两种双塔精馏工艺而言,分割式热泵精馏工艺较双效热集成精馏工艺,可节约设备投资费用约2.69%,年运行总费用节约17.33%。     

A reactive distillation column with double reactive sections for the separations of two-stage consecutive reversible reactions

In this paper, a novel reactive distillation column with double reactive sections (RDC-DRS) is proposed for the separations of two-stage consecutive reversible reactions. The arrangement of two reactive sections not only allows the careful coordination of the two reaction operations involved, but also provides additional degrees of freedom for the reinforcement of internal mass integration and/or internal energy integration between the reaction operations and the separation operation involved, which could facilitate the RDC-DRS to be more advantageous than the conventional reactive distillation column with a single reactive section (RDC-SRS) in operating cost and capital investment. A representative hypothetical and real two-stage consecutive reversible reactions are chosen to evaluate the steady-state performance of the RDC-DRS. With the constraints of the same total number of stages and the same total number of reactive stages, the RDC-DRS is demonstrated to require less utility consumption than the RDC-SRS and this outcome indicates that the former could be a competitive alternative to the latter in the separations of the two-stage consecutive reversible reactions. The number of reactive sections should therefore be viewed as an important decision variable for the synthesis and design of reactive distillation columns especially in the separations of complicated reacting mixtures involving multiple reversible reactions.     

Optimal operation strategy of batch vacuum distillation for sulfuric acid recycling process

Vacuum distillation techniques are widely used in food, biological, pharmaceutical, and wastewater treatment industries. Because of its operation at low temperatures, vacuum distillation prevents the thermal decomposition of materials and alleviates corrosion processes; however, condenser size can be dramatically increased because of reductions in mean temperature differences under the vacuum operation. In batch vacuum distillation processes, vapor generation rate and mean temperature differences are changed with time. In view of these characteristics of batch operation, this paper suggests a novel methodology to minimize the condenser size in batch vacuum distillation processes. The target process is a sulfuric acid recycling system in semiconductor manufacturing plants. In this paper, an equation-oriented dynamic model is established and optimization problem is formulated. By solving the nonlinear programming problem, the condenser size is dramatically reduced when operation time is fixed. In contrast, operation time is greatly shortened when the installed condenser surface area is fixed.     

内部热耦合精馏塔的操作性能与模拟

对同轴式内部热耦合精馏塔的操作性能和节能效果进行了研究,考察了全回流操作条件下,压缩比对回流量、冷凝器负荷和再沸器负荷的影响。结果表明,随着压缩比的增大,回流量、冷凝器负荷和再沸器负荷均降低。通过实验数据计算得到了该塔的理论板数和两塔间的传热量,精馏段为9块理论板,提馏段为4块理论板,当压缩比为2.2:1时,两塔间传热量为9.98kW。连续操作条件下,对内部热耦合精馏塔的节能效果进行了分析,通过与常规精馏塔的比较,内部热耦合精馏塔可节约52.3%的冷量,输入的再沸器和压缩机总负荷可节约20.34%。另外,基于实验数据,对该内部热耦合精馏塔进行了动态模拟,经连续操作下的实验验证,该内部热耦合精馏塔可在2h后达到稳定操作。     

A note on the identification and control of batch distillation columns

A method for the identification and control of a batch distillation process is presented in this note. The proposed model consists of a first-order integrating process in composition with a high-frequency gain. The feedback controller is designed in the framework of robust nonlinear control with modeling error compensation techniques for the control of distillate composition via manipulations of the reflux ratio. The proposed identification and control procedures are illustrated via numerical simulations.     

同轴式内部热耦合精馏塔的传热性能

提出了一种以实验物系的物性数据为基础的计算同轴式内部热耦合精馏塔（HIDiC）总传热系数的方法。本文以乙醇-水为实验物系,以自行搭建的中试规模同轴式HIDiC为研究对象,通过在不同压缩比下（1.4~2.6,步长为0.1）的连续操作实验研究,得到塔内的温度分布,通过计算两塔段的相变给热系数来计算该塔的总传热系数和精馏塔段与提馏塔段间的换热量。在同轴式HIDiC中乙醇-水实验物系总传热系数的计算值在300~800W/(m²·K),并且随着压缩比的增大而逐渐降低。在操作条件和产品纯度与实验值保持一致的情况下,将精馏塔段与提馏塔段间换热量的计算值带入软件中模拟,得到的全塔温度分布与实验中的温度分布在误差范围内吻合良好,证明本文计算同轴式HIDiC总传热系数的方法切实有效。