Time optimal start-up strategies for reactive distillation columns

In this contribution, a rigorous process model to simulate the start-up of a cold and empty reactive distillation (RD) column is developed and experimentally validated with a transesterification process. Strategies for time optimal start-up of an RD column are presented. The mostly used strategy for conventional distillation of total reflux for RD is only recommendable with limitations. New, alternative strategies, like the recycling of the off-spec bottom and top product or the initial charging with product, to minimize the necessary start-up time are presented. Suitable strategies can save up to 82% of the needed time for the column start-up.     

Effects of Liquid Holdup in Condensers on the Start‐Up of Reactive Distillation Columns

Compared with start‐ups in conventional distillation columns, those in reactive distillation (RD) columns are much more time and energy consuming, and generate a large amount of by‐products which are not easy to deal with together. For several years, researchers have been trying out different methods to shorten the time required to lower the cost of the start‐up. In this work, a rigorous dynamic model in the ChemCAD simulator is applied to model the start‐up process for the esterification of ethyl acetate in a reactive distillation column. In the model, two sets of equations are employed: one for the fill‐up and heating stage and the other for the equilibration process which follows. In the fill‐up and heating stage, fluctuation curves of the reboiler temperatures with respect to time which are similar to those for conventional distillation columns are observed, while in the equilibration process it is found that the increase of the liquid holdup volume in the condenser reduces the time required to reach steady state for the reactive column and decreases the liquid holdup volume in the reboiler at the equilibrium state. This shows that the liquid holdup volume in the condenser has an important effect on the start‐up of reactive distillation columns.     

反应精馏过程中的多稳态分析

Reactive distillation processes for synthesis of ethylene glycol （EG） and ethyl tert-butyl ether （ETBE） were modeled with the simulation package ASPEN PLUS. The input multiplicity and output multiplicity were discussed with the method of sensitivity analysis for both cases. In EG production process, steady state multiplicities were studied in terms of effective liquid holdup volume and boil-up ratio. In ETBE synthesis process, the user kinetic subroutine was supplied into ASPEN PLUS firstly, and then the composition, temperature and reaction-rate profiles within the reactive distillation column were presented in detail. A set of stable solution branches based on distinct initial guesses for a range of boil-up ratio were found in EG synthesis. Input multiplicities were observed for a range of reboiler duty at several values of reflux ratio for ETBE synthesis process. These results can be used to avoid excessive energy consumption and achieve optimum design of reactive distillation column.     

Predictions for Start‐Up Processes of Reactive Distillation Column via Artificial Neural Network

The time consumed in starting up the unit with appropriate holdups can form an important part of the total distillation time, particularly for reactive distillation systems with large holdups. Also, the products formed during the start‐up time are off specification, and are not easily recycled as for traditional distillation, but must be carefully disposed of, which can be very costly. A back‐propagation algorithm artificial neural network model is presented as a tool to assess the start‐up process for a given reactive distillation system. All the data required for training and testing the artificial neural network have been generated using the CHEMCAD simulator, version 5.2–0. The values for the learning rate, momentum term, and gain term of the artificial neural network have been taken as 0.01, 0.6, and 1.0, respectively. From the case studied in this work, it can be seen that a good start‐up policy can reduce both the energy and time requirements in the start‐up phase of reactive distillation processes. Results from predictions show the time consumed in the start‐up period has an average error of 2.833 %, and a maximum error of 7.600 %, for the case studied here. The accuracy of the model will depend upon the data available and the type of model being approximated.     

Control System Design for a Single Feed ETBE Reactive Distillation Column

Reactive distillation (RD) is advantageous for the Ethyl Tert‐Butyl Ether (ETBE) synthesis. The steady state model of an ETBE reactive distillation column created using the simulator HYSYS is analyzed to synthesize effective control structures. Since the column exhibits input multiplicity with the dual process objectives of ETBE RD (isobutene conversion and ETBE purity), inferential variables are selected. A control structure that organizes a sensitive tray temperature in the stripping section using the reboiler duty and maintains the temperature difference of reactive trays using the reflux flow, is found to be most suitable. A decentralized PI controller and constrained Model Predictive Controller (MPC) are implemented, and performances are compared for set point tracking and disturbance rejection. MPC control algorithms are implemented in MATLAB and interfaced with HYSYS. Constrained MPC (CMPC) is found to be effective for load disturbance rejection, which frequently occurs in the single feed configuration.     

Multiple Analysis in a Reactive Distillation Column for the Synthesis of tert‐Amyl Methyl Ether

tert‐Amyl methyl ether (TAME) is produced via reactive distillation. A simulation is set up and controlled on Aspen HYSYS v 8.0 for generating the highest purity of TAME. This simulation includes a plug‐flow reactor and a reactive distillation column. Emphasis was put on finding the optimal operating conditions of the reactive distillation column in order to get the maximum purity of TAME. The operational parameters were reflux ratio, number of reactive stages in the distillation column, and condenser pressure. The results indicated the optimal reflux ratio and condenser pressure which could be adapted to industrial scale.     

An Extensive Analysis on the Start‐up of a Simple Distillation Column with Multiple Steady States

The impact of start‐up procedures on the behaviour of simple distillation columns with multiple steady states is analyzed. A well‐known system with hysteresis is studied in this paper and transient responses for a binary distillation column yielding different steady states during the start‐up operation are shown. Several dynamic simulation results showing an interesting behaviour are presented. Through the examination of the profile evolutions corresponding to given start‐up policies, it can be seen how the column arrives to different steady states. It is shown that it is possible to identify a set of critical values for the start‐up supervision. Also, guidelines of general validity are achieved with the aim of finding the appropriate start‐up policy to obtain the desired solution.     

Strategies for Starting Up Azeotropic Distillation Columns with Multiple Steady States

The operability of azeotropic distillation columns with multiplicity is analysed during start‐up by dynamic simulation. Different steady states can be reached by applying different start‐up configurations and/or policies. The well‐known benzene‐heptane‐acetone (BHA) system is studied. The process by which the column reaches these steady states can be seen through the examination of profile evolutions corresponding to the given start‐up policies. Indeed, a clear partition of the start‐up policies space yielding different solutions is achieved. Some properties of this space are explained and start‐up critical values can be identified. Finally, some guidelines for start‐up supervision are outlined for the study case.     

Transesterification of methyl myristate in a continuous reactive distillation column: simulation and experiment

The transesterification of methyl myristate with isopropanol to methanol and isopropyl myristate is presented. This reactive system is suitable for reactive distillation and is used for the investigation carried out in this paper. A simulation model for the steady state and dynamic simulation of the reactive distillation processes was developed. For the validation of this model experiments were carried out. Based on dimensioning calculations, a 6 meter high reactive distillation column (0.1 m i.d.) with 22 bubble cap trays and a total liquid holdup of about 10 litres was constructed and built up. The stationary results obtained from the column show a good comparison between the simulated and the experimental concentration and temperature profiles. The experimentally determined dynamic time constants and sensitivities of the temperature profile of the column could be reproduced very well by the simulation tool developed.     

Enzymatic catalyzed reactive dividing wall column: Experiments and model validation

A novel process for the integration of chemical reaction and product separation is proposed: the enzymatic catalyzed reactive dividing wall column (eRDWC). The eRDWC combines the highly integrated and complex reactive dividing wall column (RDWC) with the use of a very selective enzymatic catalyst. This apparatus enables the simultaneous production and separation of up to 4 pure product streams. Comprehensive experiments with the reference system of a hexanol and butyl acetate transesterification in a DN 65 pilot scale column show the feasibility of stable steady state operations for this process. A rigorous model for the plant design of an eRDWC wall column is developed. The reaction kinetics and vapor‐liquid‐equilibria for the reference system are measured and implemented in the model. The model is successfully validated using the acquired experimental data. The application of enzymes in continuous reactive distillation processes has the potential to increase the selectivity at milder process conditions. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2198–2211, 2017     

侧反应器反应精馏方法生产醋酸甲酯的模拟

采用强酸性阳离子交换树脂催化醋酸与甲醇反应精馏生成醋酸甲酯,可避免硫酸作为催化剂的不足。但该非均相催化反应受平衡限制,且达到平衡时间较长,采用传统反应精馏塔难以提供足够反应空间。文中设计侧反应器与精馏塔耦合新工艺,采用Aspen Plus软件模拟研究了侧反应器数量、位置,原料进料位置,回流比,醇酸比等对反应精馏过程的影响。结果表明,当装置具有7个侧反应器,反应器间隔4块板,在优化的操作条件下,醋酸甲酯质量分数可达99.1%。     

On the multiple solutions of the reactive distillation column for production of fuel ethers

A systematic study of the operating conditions and parameter sensibility of multiple steady states in a reactive distillation column for production of fuel ethers is presented. The multiplicity analysis is performed using bifurcation diagrams for several scenarios using the process simulator Aspen One Aspen Plus. Our results indicate that the main variables that affect both the presence and behavior of multiple solutions in the reactive distillation column are the reflux ratio, the reboiler duty and the thermal condition in the feed stream. In particular, we have determined that the vapor–liquid stream in the feed has a major influence on the occurrence of this phenomenon and this parameter especially establishes the type of multiplicity that can occur in the reactive distillation column for production of fuel ethers.     

A novel process for the synthesis of unsaturated polyester

Traditionally polyester production is done in a batch reactor equipped with a separation column for a batch distillation. A promising alternative for the intensification of this process is reactive distillation. The aim of this paper is to study the conceptual design of reactive distillation and to find out whether reactive distillation is potentially interesting compared to batch reactor process. Therefore, a reactive distillation model is developed and sensitivity analysis is used to obtain the design and operational parameters for the reactive distillation process. These parameters are the required number of stages, required residence time, feed ratio, reflux ratio and temperature of feed stream. The model predicts the polymer attribute, isomerization and saturation composition of the polymer in the range of industrial polyester production data. The simulation study shows that the total production time of polyester in a continuous reactive distillation system is reduced from 12 h to 1.5-2 h compared to the industrial batch reactor process. The equilibrium conversion is also raised by 7% compared to the conventional process. The model demonstrated that reactive distillation has the potential to intensify the process by factor of 6-8 in comparison to the batch reactor.     

Heterogen katalysierte Reaktivdestillation: Design und Scale‐up am Beispiel von Methylacetat

Reactive Distillation by Heterogeneous Catalysis: Design and Scale‐up Using Methyl Acetate as an Example Methyl acetate synthesis and hydrolysis is used to exemplify the design and scale‐up of heterogeneously catalyzed reactive distillations using Katapak‐S/‐SP. Different equilibrium and non‐equilibrium stage models and a rate‐based model are compared in order to clarify the level of complexity needed to predict the process behavior. An equilibrium stage model accounting for reaction kinetics is the best choice for methyl acetate reactive distillation. Reliable information on fluid dynamics of the used reactive distillation packing is needed for the fluid dynamic design in order to assure a wide operation range of the reactive distillation column. To verify the process model, experiments on the synthesis of methyl acetate have been performed in columns with different diameters. As a case study, the model‐based scale‐up is described for an industrial methyl acetate hydrolysis process.     

Design and Control of Ionic Liquid‐Catalyzed Reactive Distillation for n‐Butyl Acetate Production

A simulation study of n‐butyl acetate production with the [Hpy][HSO₄] ionic liquid catalyst was performed. Due to the lack of phase equilibrium data, the binary interaction parameters of the NRTL model for ionic liquid and reactive species were calculated by the COSMO‐RS technique. A reactive distillation process with recycled ionic liquid stream was proposed, and the column configuration was optimized by minimization of the total annual capital. The novel process is considerably efficient and economic compared to the traditional reactive distillation process of nonionic liquids. With the steady‐state parameters, a plant‐wide control structure was further developed to evaluate the robustness of the control system by exerting the disturbances of feed flow rate and feed composition. Dynamic simulation results suggest that the control scheme with a composition controller is timely and effective.     

Investigations on the Synthesis of Methyl Acetate in a Heterogeneous Reactive Distillation Process

The production of methyl acetate in a reactive distillation process – prior art for 15 years – is often used as an example to study the basic phenomena of reactive distillation. The present paper deals with a theoretical and experimental analysis of methyl acetate synthesis in a reactive distillation column. A design method based on the interpretation of reactive distillation line diagrams is used to identify the main process parameters and to provide a foundation for experimental investigation. The significant influence of the reflux ratio on the conversion in the column is shown by mini plant experiments using supported ion exchanger in the form of Raschig rings as a heterogeneous catalyst. These experiments demonstrate the catalytic quality of this packing material. To simulate the reactive distillation column with a simple stage-to-stage method, the separation efficiency of the catalytic rings is investigated. Comparison of experimental and simulation results reveals that a simple model based on the assumption of simultaneous chemical and phase equilibrium describes the experimental data quite well over a wide range of reflux ratios. Furthermore, simulation results show that the conversion depends less on the number of reactive stages than on the use of two feed stages.     

间歇蒸馏的新设计法

本文提出间歇塔的一种新的设计方法——序列稳态塔法。用此法可同时求出间歇蒸馏塔的理论板数、最佳操作回流比、塔釜组成和温度随时间的变化;导出釜液温度与最佳操作回流比的关系,实现由釜液温度前馈控制整个间歇蒸馏过程;以及求出整个间歇蒸馏过程所需的时间。计算速度快,其结果可满足工程设计的需要。     

A globally convergent method for finding all steady‐state solutions of distillation columns

A globally convergent method is proposed that either returns all solutions to steady‐state models of distillation columns or proves their infeasibility. Initial estimates are not required. The method requires a specific but fairly general block‐sparsity pattern; in return, the computational efforts grow linearly with the number of stages in the column. The well‐known stage‐by‐stage (and the sequential modular) approach also reduces the task of solving high‐dimensional steady‐state models to that of solving a sequence of low‐dimensional ones. Unfortunately, these low‐dimensional systems are extremely sensitive to the initial estimates, so that solving them can be notoriously difficult or even impossible. The proposed algorithm overcomes these numerical difficulties by a new reparameterization technique. The successful solution of a numerically challenging reactive distillation column with seven steady‐states shows the robustness of the method. No published software known to the authors could compute all solutions to this difficult model without expert tuning. © 2013 American Institute of Chemical Engineers AIChE J 60: 410–414, 2014     

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。     

基于优化的反应精馏塔简捷设计

基于G ibbs自由能最小原理达到反应和相平衡的假设,提出了一种适用于初步设计的新的设计方法。以甲基叔丁基醚和碳酸二乙酯的反应精馏过程为例,应用Aspen软件模拟,经分析发现,通过改变理论级数和回流比,可得到合理的塔内温度分布,从而使塔底产品组成得到最大程度的提高,为此提出基于优化的设计法:以产品组成最大为目标函数,以回流比、精馏段和提馏段理论板数为决策变量,采用遗传算法进行优化计算。结果表明,2个设计实例均能在保证低能耗的同时得到较高的产品纯度,说明该设计方法可以设计出较好的反应精馏塔。