Analysis of the Start‐up Process for Reactive Distillation

The start‐up procedure of a distillation column is a time‐ and energy‐consuming process. Further, the products during the start‐up time are off specification and cannot easily be recycled as for conventional distillation but must costly be disposed of. In this paper, a process model to simulate the barely analyzed start‐up procedure for a reactive distillation from the cold and empty state to steady state is presented. The start‐up of a reactive distillation column has been modeled with gPROMS. The advantage of a cold and empty start‐up is the consistent and reproducible initialization. Commercial simulators do not give the opportunity to start form a cold and empty state, e.g., a column modeled with Hysys must be shut down from a steady state to be able to model the complete start‐up process, which is not possible, for example, for a batch process. Also, a change in the describing equations and discontinuities in process variables is difficult to handle within the simulation. In this paper, the start‐up strategies normally used for distillation without reaction are examined and applied to reactive distillation. It will be shown that the widely used strategy of total reflux is not suitable for reactive distillation. A simplified model to derive a time constant which describes the influence of parameter setting changes, like heating power, reflux ratio and feed composition on the start‐up time, is introduced and validated.     

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.     

In‐Line Monitoring of Crystallization Processes Using a Laser Reflection Sensor and a Neural Network Model

Laboratory‐scale experiments were carried out for measuring the chord length distribution of different particle systems using a laser reflection sensor. Samples consisted of monodisperse, polydisperse and bimodal FCC catalyst and PVC particles of different sizes, ranging from about 20 to 500 μm. The particles were dispersed in water, forming suspensions with solid‐phase mass fractions ranging from ca. 0.2 % until ca. 30 %. The experimental results, consisting of the particle number counting per chord length class, were used in fitting a neural network model for estimating the mass concentration of particles in the suspension and the volume‐based size distribution, eliminating the effects of suspension concentration and particle shape. The results indicate the feasibility of using such a model as a software sensor in crystallization processes monitoring.     

Implementation and Operation of a Dividing‐Wall Distillation Column

The design and construction of a prototype of a dividing‐wall distillation column was possible by integrating previous knowledge in process intensification, energy savings, theoretical control properties, and closed‐loop dynamics of thermally coupled distillation sequences. In order to achieve the predicted energy savings for this class of complex distillation column, a dividing wall and a side tank were implemented in order to manipulate the internal flows associated with energy consumption. The reaction between ethanol and acetic acid was conducted within the prototype, and the experimental results indicate that a heterogeneous mixture of ethyl acetate and water is obtained as the top product. The temperature profile measured during the experimental run can be used for controlling the batch distillation column in cyclic operation mode.     

Conceptual Design of Double‐Feed Reactive Distillation Columns

The feasibility and feasible range of operating parameters for double‐feed reactive distillation columns are evaluated, based on the combination of pinch point map analysis for the middle‐section in the compositional space and the feed angle method as an efficient shortcut design method. Limiting bounds for operating parameters are determined where the properties of singular points change. The existence and values of such bounds may vary in double‐feed reactive distillation columns depending on the nature of the system under study. The methodology is illustrated by production of methyl acetate and ethyl acetate. An efficient method is described to identify the most promising candidates of double‐feed reactive distillation columns and to study the design flexibility in terms of operating parameters.     

On‐Line Detection of Contamination in a Bioprocess Using Artificial Neural Networks

Fermentation is a very important bioprocess for the production of drugs, food products, beverage and for animal cell line culture etc. The substrates used in these processes are expensive. So on‐line monitoring of contamination in a fermentation process is very essential in industries. A new method for contamination detection is being proposed in this paper. This is a software‐based method. In this new method, the state variables of the process are used to detect contamination of the process.     

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.     

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.     

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.     

连续反应精馏合成乙酸异丙酯

以乙酸和异丙醇为原料通过连续反应精馏合成乙酸异丙酯,实验研究了影响反应的因素,结果表明最佳合成条件为：酸醇比1：1．2,回流比3,异丙醇的进料流量2mL／min,硫酸用量为乙酸体积的2％,乙酸异丙酯的最大收率为92．5％。     

Prediction via Neural Networks of the Residual Hydrogen Peroxide used in Photo‐Fenton Processes for Effluent Treatment

This communication proposes the use of neural networks in the prediction of residual concentrations of hydrogen peroxide from the treatment of effluents through Advanced Oxidative Processes (AOP's), in particular, the photo‐Fenton process. To verify the efficiency of the oxidative process, the Chemical Oxygen Demand (COD) parameter, the values of which may be modified by the presence of oxidizing agents such as residual hydrogen peroxide, is frequently taken in account. The analysis of the H₂O₂ interference was performed by spectrophotometry at 450 nm wavelength, via the monitoring of the reaction of ammonia with metavanadate. The results of the hydrogen peroxide residual concentration were modeled via a feedforward neural network, with the correlation coefficients between actual and predicted values above 0.96, indicating good prediction capacity.     

乙酸乙酯反应精馏生产工艺模拟研究

以实际生产数据为基础,运用化工稳态模拟计算软件ASPEN PLUS,在建立现有乙酸乙酯酯化工艺仿真模型的基础上,对现有工艺进行改进,采用催化剂循环的方式,建立了生产乙酸乙酯的反应精馏新体系的计算机仿真模型。模拟研究结果表明：乙酸乙酯的带循环反应精馏新工艺是可行的,在相同的进料条件、相同的设备规格下,相比于现有生产工艺,新工艺提高生产能力约24％,同时降低了能耗和节省了设备投资。     

Explicit Nonlinear Predictive Control of a Distillation Column Based on Neural Models

A nonlinear Model Predictive Control (MPC) algorithm and its application to a distillation column are described. The algorithm uses a neural model of the process that is linearized online around the current operating point. The algorithm is computationally efficient because the control policy is calculated explicitly without any optimization. The algorithm requires online repetition of a matrix decomposition task and the solution of linear equations. The obtained solution is projected onto the admissible set of constraints imposed on the magnitude and the increment of the manipulated variables. For the distillation column considered, the control accuracy is comparable not only to that obtained in MPC with online linearization and quadratic programming but also to that obtained in nonlinear MPC, which is based on full nonlinear optimization repeated at each sampling instant.     

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.     

基于神经网络的软测量技术在精馏塔上的应用

针对扬子石化公司丁二烯精馏塔原控制系统存在的问题, 利用从集散控制系统(DCS)采集的大量现场数据和用机理模型得到的模拟数据, 运用前向反馈(BP)神经网络软测量技术,构造了产品丁二烯和总炔含量的自适应软测量仪表, 设计了一套控制系统. 实际监测数据表明, 这套控制系统可实现产品质量的闭环控制.     

Reactive Distillation for Solvent Regeneration after Biphasic Carboxylic Acid Esterification

Emulsion-enhanced biphasic esterification has proven to be applicable for carboxylic acid recovery from dilute aqueous process streams. The carboxylic acid is esterified with 1-octanol in an emulsified regime with 4-dodecylbenzenesulfonic acid (4-DBSA) or Ni(DBSA)₂ as catalyst. After phase separation, the laden solvent phase must be regenerated. This study presents a regeneration concept based on reactive distillation with transesterification of the octyl ester-laden solvent with methanol. The regenerated solvent is reused in the extraction step.     

全回热反应蒸馏塔的动态特性研究

摘要全回热反应蒸馏塔的反应操作和分离操作过程具有特殊的欠阻尼特性,而通过严格的再沸器液位控制可以使欠阻尼效果基本消除。以A和B反应生成C来说明了理想全回热反应蒸馏塔的这种动态特性。     

Hydrodynamics of Distillation Tray Column with Structured Catalyst Containing Envelopes: Experiments versus CFD Simulations

We report studies on the hydrodynamics of a distillation sieve tray column in which structured catalyst containing wire‐gauze envelopes are dispersed along the liquid flow direction. The gas and liquid phases are in cross‐current contact on the tray and were studied using Computational Fluid Dynamics (CFD). Experiments were carried out to determine the clear liquid height on a rectangular tray as a function of geometry and operating conditions. The agreement between the experiments and CFD simulations was found to be very good, suggesting that CFD simulations can be used for design and scale‐up purposes.     

Entrainer selection for the synthesis of fatty acid esters by Entrainer-based Reactive Distillation

In this research it is demonstrated that, due to the similarities between Entrainer-based Reactive Distillation and azeotropic distillation, the same selection rules can be applied to select a suitable entrainer. From a list of suitable entrainers for the azeotropic distillation of isopropanol and water, cyclohexane and isopropyl acetate are chosen. Residue curve maps, simulations of the distillation section of the column, and simulations of the total Entrainer-based Reactive Distillation concept show that both can be used as an entrainer in Entrainer-based Reactive Distillation. Whether the Entrainer-based Reactive Distillation concept will be feasible, depends strongly on the kinetics of the reaction.