A molecular design method based on the COSMO‐SAC model for solvent selection in ionic liquid extractive distillation

In this study, a molecular design method was used to select solvents for extractive distillation. A COSMO‐SAC model was used to screen for prospective solvents from a wide variety of ionic liquids for extractive distillation. Based on the COSMO‐SAC model, the σ‐profile database of ILs was established. Selectivity and solubility were used as the indexes for solvent screening. According to the molecular design method, three suitable extractive distillation solvents were determined for acetonitrile‐water and ethanol‐cyclohexane systems. Vapor ‐ liquid equilibrium experiment were used to test chosen ILs. This study showed that the experimental and design results were consistent with each other. Therefore, this method is effective and applicable to pick ILs solvents for extractive distillation, and the results could provide a theoretical foundation for industrial production. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2853–2869, 2016     

A novel type of equipment for reactive distillation: Model development,simulation, sensitivity and error analysis

A simulation study of heterogeneously catalyzed reactive distillation experiments carried out with the D + R tray, a novel type of laboratory equipment, is presented. One advantage of the D + R tray is that reaction and distillation are alternating stage‐wise, in a well‐defined way that can be modeled straightforwardly. An equilibrium stage model is used to describe the distillation and a plug flow reactor model to describe the catalyst bed reactors. The model parameters are derived from a systematic experimental characterization of the D + R tray both as a reactor and as a distillation unit. A validated physicochemical fluid property model is used. The primary experimental data are reconciled. Results from the predictive simulations are in good agreement with the experimental results. The influence of errors in the input parameters on the simulation results is investigated by means of a sensitivity and error analysis. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1533–1543, 2013     

共沸精馏分区特性的研究

简单蒸馏剩余曲线区域边界可近似描述连续共沸精馏的分区特性。提出确定共沸精馏分区边界位置的数学模型,以乙醇-氯仿-丙酮三元物系为例进行了计算,并用连续精馏塔实测浓度分布数据验证计算结果的可靠性和实用性。     

Experimental validation of a flexible modeling approach for distillation columns with packings

The two main concepts for the modeling of distillation columns are the equilibrium‐stage (EQ) and the nonequilibrium‐stage (NEQ). A model is presented which combines decisive features of both conventional concepts. Based on the idea of a reduced nonequilibrium‐stage (RNEQ), this model can be used for the simulation of distillation columns with packings. In contrast to the conventional NEQ approach, this model neglects the influence of liquid side mass‐transfer coefficients, which ultimately allows to come up with only one empirical equation describing the overall mass transfer. Thus, a considerable reduction in model complexity is reached, which allows for an efficient consideration of new experimental distillation results. Fitted to experimental data, the model is able to predict, how different pressures and chemical systems might affect the separation efficiency. By comparing calculation results with experimentally determined separation efficiencies for three different packing types, these valuable RNEQ qualities are illustrated. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3833–3847, 2014     

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.     

Concentration of Natural Vitamin E Using a Continuous Countercurrent Supercritical CO2 Extraction‐Distillation Dual Column

A continuous countercurrent supercritical CO₂ extraction‐distillation dual‐column process was developed to extract and concentrate natural vitamin E (VE) from soybean oil deodorizer distillate (SODD). The experimental results demonstrated that process parameters such as extraction pressure, temperature, and solvent‐to‐feed ratio significantly impacted on the extraction efficiency of natural VE. A new five‐parameter mass transfer model for the continuous countercurrent supercritical CO₂ extraction‐distillation dual‐column process was presented based on the Penetration and Double‐Film theories. The calculated values of the mathematical model agreed well with the experimental data, with absolute average relative deviation values of less than 25 %.     

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.     

Simulation of Membrane Distillation for Purifying Water Containing 1,1,1‐Trichloroethane

Vacuum membrane distillation is modeled for the purification of water containing organic matter. The separation medium is a hollow‐fiber membrane contactor that is simplified to a two‐dimensional structure with a single porous membrane wall. The model considers the transport phenomena of a vacuum membrane distillation system in porous media, in which the aqueous volatile organic solution was considered as an incompressible and steady fluid. The numerical simulation of the two‐dimensional model of vacuum membrane distillation for an aqueous solution of 1,1,1‐trichloroethane was established under steady state. The effects of the bulk feed temperature and the feed flow rate on the percentage of 1,1,1‐trichloroethane removal from an aqueous solution are discussed.     

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.     

Rigorous design of distillation columns using surrogate models based on Kriging interpolation

The economic design of a distillation column or distillation sequences is a challenging problem that has been addressed by superstructure approaches. However, these methods have not been widely used because they lead to mixed‐integer nonlinear programs that are hard to solve, and require complex initialization procedures. In this article, we propose to address this challenging problem by substituting the distillation columns by Kriging‐based surrogate models generated via state of the art distillation models. We study different columns with increasing difficulty, and show that it is possible to get accurate Kriging‐based surrogate models. The optimization strategy ensures that convergence to a local optimum is guaranteed for numerical noise‐free models. For distillation columns (slightly noisy systems), Karush–Kuhn–Tucker optimality conditions cannot be tested directly on the actual model, but still we can guarantee a local minimum in a trust region of the surrogate model that contains the actual local minimum. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2169–2187, 2015     

A continuous‐effect membrane distillation process based on hollow fiber AGMD module with internal latent‐heat recovery

A continuous‐effect membrane distillation (CEMD) process was developed by equipping air gap membrane distillation (AGMD)‐based and strictly‐parallel hollow fiber module with internal heat recovery. Its performance was indicated by flux, performance ratio and evaporation efficiency. Two kinds of CEMD modules made from different membrane fibers were tested. A face‐centered central composite experimental design was conducted to investigate the influences of operating variables including cold‐feed temperature, hot‐feed temperature, and feed‐in flow rate on the performance. Within the studied experimental range, the maximum PR of 13.8 was obtained. A theoretical model based on governing transport equations was established to predict the process performance, and the model described the experimental data fairly well. In light of the model, possible ways to further increase PR were predicted. The dilute aqueous sugar solution was successfully concentrated 12‐fold to a final concentration of about 20 wt % by using CEMD process with a final PR of 8.2. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1278–1297, 2013     

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.     

Trennleistung von Dünnschichtverdampfern

The evaporation process has recently gained new momentum through special applications in chemical engineering and especially in environmental engineering, e.g. in the recovery of materials of value from liquid production residues. Thin‐layer evaporators with rotating wipers are particularly suitable for such tasks if the products of interest are thermally unstable or are prone to crusting. If these applications involve distillation‐type separation then a knowledge of the expected separation effect is important for calculations. This article aims to make a contribution to this topic. It is based on experimental studies performed on a laboratory‐scale thin‐layer evaporator and on earlier treatments of the theory of distillation in thin‐layer evaporators with a mechanically generated liquid film.     

Computational Approach to Characterize the Mass Transfer between the Counter‐Current Gas‐Liquid Flow

Structured packed columns are widely used in the chemical industry for distillation and absorption. However, the understanding of the transfer mechanism behind the counter‐current gas‐liquid flow in structured packed columns is still limited. In this work, a three‐dimensional CFD model that considers the local absorption and the local momentum transfer mechanism is developed for a film flow on a small plate with a counter‐current gas flow. The model, based on the Volume of Fluid (VOF) method, is built up on the basis of a pressure drop model and the penetration theory to quantitatively investigate the instantaneous hydrodynamics and mass transfer characteristics of the liquid phase. Simulations and experiments are carried out for a system consisting of propane and toluene. A comparison of the simulation results with the experimental data for the outlet concentrations shows good agreement.     

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.     

Thermooxidative stability of vegetable oils refined by steam vacuum distillation and by molecular distillation

Semi‐refined rapeseed and sunflower oils after degumming and bleaching were refined by deodorization and deacidification in two ways, i.e., by steam vacuum distillation in the deodorization column Lurgi and by molecular distillation in the wiped‐film evaporator. The oxidative stability of the oils before and after the physical refining has been evaluated using non‐isothermal differential scanning calorimetry. Treatment of the experimental data was carried out by applying a new method based on a non‐Arrhenian temperature function. The results reveal that refining by molecular distillation leads to lower oxidative stability of the oils than refining by steam vacuum distillation. Practical applications : (i) A method for the refining of edible oils by the molecular distillation in the wiped film of a short‐path evaporator is presented and applied. (ii) Oxidative stability of the oils refined by molecular distillation and steam vacuum distillation is compared. It has been found that refining by molecular distillation leads to lower oxidative stability of the oils than refining by steam vacuum distillation. (iii) Experimental data were treated by applying a new method based on a non‐Arrhenian temperature function. The method enables trustworthy predictions of oil stabilities for the application temperatures.     

Recovery of lactic acid by batch reactive distillation

Lactic acid, being virtually a non‐boiling compound, is difficult to separate from its aqueous solution by conventional methods such as distillation. It is necessary to convert it to the relatively volatile ester and the separation of the ester, followed by hydrolysis, is recommended as an appropriate method of recovery. In the present work, we explore and investigate a novel reactive distillation strategy to perform esterification, distillation and hydrolysis in a single unit. The experiments were performed in a batch reactive distillation set‐up and the results have been explained with the help of an appropriate model. An unsteady state mathematical model based on an equilibrium stage concept was developed for batch reactive distillation. A pseudo‐homogeneous model was used for the determination of reaction kinetics. The effect of operating parameters such as feed concentration, mole ratio, catalyst loading, boil‐up rate, etc. on the recovery of lactic acid was studied with the help of simulation and experimental results. The feasibility issue of reactive distillation has been discussed based on the results obtained. Copyright © 2006 Society of Chemical Industry     

Modeling and analysis of conventional and heat‐integrated distillation columns

A generic model that can cover diabatic and adiabatic distillation column configurations is presented, with the aim of providing a consistent basis for comparison of alternative distillation column technologies. Both a static and a dynamic formulation of the model, together with a model catalogue consisting of the conventional, the heat‐integrated and the mechanical vapor recompression distillation columns are presented. The solution procedure of the model is outlined and illustrated in three case studies. One case study being a benchmark study demonstrating the size of the model and the static properties of two different heat‐integrated distillation column (HIDiC) schemes and the mechanical vapor recompression column. The second case study exemplifies the difference between a HIDiC and a conventional distillation column in the composition profiles within a multicomponent separation, whereas the last case study demonstrates the difference in available dynamic models for the HIDiC and the proposed model. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4251–4263, 2015     

Dehydration of Methanol to Dimethyl Ether by Catalytic Distillation

The kinetics of liquid catalytic dehydration of methanol over an ion exchange resin (Amberlyst 35) has been determined for the temperature range 343 to 403 K using a batch reactor. The experimental data are described well by an Eley‐Rideal type kinetic expression, for which the surface reaction is the rate‐determining step. A catalytic distillation process for methanol dehydration to dimethyl ether (DME) has been modeled using the experimentally determined kinetic data. The results were incorporated into the rate‐controlled reaction mode for RadFrac, a part of the commercial simulation program Aspen Plus. It was shown that synthesis of high purity DME can be achieved using a single catalytic distillation column. Thus there is significant potential for reduction of overall capital cost for a plant for methanol dehydration to DME when compared to conventional production facilities that involve separate reaction and distillation processes.     

Experimental operation of a reactive dividing wall column and comparison with simulation results

Reactive dividing wall columns (RDWC) are a special type of distillation column that allow for the targeted realization of chemical reactions and the separation into multiple product fractions in one shell. However, despite their huge economical and ecological potentials for certain fields of application, this innovative technology has not found its way into industrial production processes yet. The very limited availability of experimental research studies verifying the prediction capabilities of respective modeling concepts for this type of distillation column might be one decisive reason for that. Therefore, the present study puts its focus on the detailed comparison between experimental operation of RDWC and the corresponding simulation results for steady‐state. For the first time, the mentioned comparison is carried out for a chemical system with non‐negligible side reactions. It is shown that even for this highly complex system, the mathematical model is capable of predicting the column operation. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1036–1050, 2017