Design and control of reactive distillation for ethyl and isopropyl acetates production with azeotropic feeds

Reactive distillations for the production of ethyl acetate (EtAc) and isopropyl acetate (IPAc) are classified as the type-II process where the first column consists of a reactive zone and a rectifying section followed by a stripper [Tang et al., 2005. Design of reactive distillations for acetic acid esterification with different alcohols. A.I.Ch.E. Journal 51, 1683-1699]. Instead of using pure alcohols and acetic acid as reactants, this paper studies the effects of reactant purity on the design and control of reactive distillation. This offers significant economical incentives (by reducing raw materials costs), because ethanol forms an azeotrope with water at 90 mol% and isopropanol/water has an azeotrope at 68%. The purities of the acid is set to 95% for acetic acid (industrial grade), 87% for ethanol, and 65% for isopropanol. The results show that the total annual costs (TAC) increase by a factor of 5% for EtAc and 8% for IPAc production using reactive distillation. Next, the operability of the reactive distillations with azeotrope feeds is explored. Three disturbances, feed flow, acid feed purity, and alcohol feed composition, are introduced to assess control performance using dual-temperature control and one-temperature-one-composition control. Simulation results indicate good control performance can be achieved for reactive distillation with azeotropic feeds.     

二异丁烯反应精馏生产过程控制策略设计

二异丁烯是一种重要的化工中间体,近年来研究者提出了以催化裂化C₄为原料、采用反应精馏技术同时生产高纯二异丁烯和汽油添加剂的新工艺。由于反应精馏过程中非线性程度高,稳定控制困难,使得采用反应精馏技术生产二异丁烯过程的控制策略研究较少。采用Aspen dynamic软件进行动态模拟,针对反应精馏生产二异丁烯过程开发了温度控制方案、组分温度联合控制方案和组分温度串级控制方案。对3个控制系统进行（±10）%的进料流量扰动和（±5）%组成扰动测试并进行对比。结果表明：组分温度串级控制方案在添加扰动的情况下依然保证了二异丁烯质量分数99%,三异丁烯质量分数小于10%以及异丁烯转化率大于99%的要求,并且最终稳定时间约5 h,具有更好的抗干扰性能。研究结果能够为二异丁烯产品的生产工艺工业化应用提供设计依据。     

A reactive distillation process with a sidedraw stream to enhance the production of isopropyl acetate

This paper designs an entrainer combined with a sidedraw to enhance the reactive distillation (RD) process of isopropyl acetate (IPAc). Acetic acid (HAc) reacts with isopropanol (IPOH) to generate IPAc and water (H₂O). The ratio of IPAc to H₂O in the products of esterification is smaller than that in the minimum boiling IPAc–IPOH–H₂O azeotrope, resulting in a mass of organic phase reflux to remove the surplus H₂O from the top of the RD column. This process consumes a high amount of energy. For better energy efficiency, a feasible design flowsheet includes an RD column, a stripper, a top decanter, a middle decanter, and a sidedraw stream to intensify the azeotropic separation where an entrainer is introduced to carry out the surplus water from the middle of the RD column in the form of a liquid phase. The key design variables in the proposed flowsheet are determined to obtain a minimal total annual cost (TAC). As a result, an optimal process design is drawn out while satisfying the stringent specifications for product purity. These results show that the energy requirements of the IPAc system can be decreased by 27.55%.     

Optimization and control of a reactive distillation process for the synthesis of dimethyl carbonate

Dimethyl carbonate is an environmentally benign and biodegradable chemical. Based on integration of reactive distillation and pressure-swing distillation technologies, a novel process for synthesis of dimethyl carbonate through transesterification with propylene carbonate and methanol has been developed by Huang et al. In this work, the optimization of this process was performed by minimizing the total TAC. The results show that the op-timal design flowsheet can save energy consumption by 18.6％with the propylene carbonate conversion of 99.9％. Then, an effective plant-wide control structure for the process was developed. Dynamic simulation results dem-onstrate that the temperature/flow rate cascade control plus with simple temperature control can keep not only product purity but also the conversion of the reactant at their desired values in the face of the disturbance in re-actant feed flow rate and feed composition.     

Application of Brönsted acid ionic liquids as green catalyst in the synthesis of 2-propanol with reactive distillation

Five Br?nsted acidic ionic liquids (ILs) were prepared and characterized by FT-IR, 1H NMR and 13C NMR. Their cat-alytic activities for the synthesis of 2-propanol (IPOH) via transesterification of isopropyl acetate (IPAc) with methanol (MeOH) were investigated. Among al the tested ILs, [Ps-mim]HSO4 performed best and was used as catalyst for further studies. The reaction kinetics were carried out to correlate the parameters in a homogeneous second order kinetic model. It has been found that there is close agreement between the calculated and experi-mental values. The high-pressure batch reactive distillation experimental apparatus was set up in order to en-hance the conversion of IPAc. A high conversion of IPAc of 99.4%was obtained under the optimal reaction conditions. The catalyst [Ps-mim]HSO4 can be recycled easily by a rotary evaporator and reused without any fur-ther treatment. The catalyst had been repeatedly used for four times and no obvious changes in the structure of catalyst could be observed.     

甲醇-苯共沸体系变压精馏分离工艺的动态控制

基于甲醇和苯共沸体系的压敏性,利用Aspen Plus和Aspen Dynamics软件对变压精馏分离该体系的稳态工艺进行了模拟和优化,研究了该工艺的动态特性,提出了控制产品纯度的3种控制结构：基础控制结构、比例控制结构和双比例与温度?组分联合控制结构,通过对控制结构添加±20%的组分和流量干扰测试控制结构的稳定性. 结果表明,基础控制结构基本能实现稳健控制,但不能解决组分干扰引起的产品纯度偏差过大等问题;比例控制结构可实现相对稳健的控制,但改进效果不显著;双比例与温度?组分联合控制结构在受到20%进料和组分干扰后,产品纯度能较快恢复至设定值的99.90%,实现稳健控制.     

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。     

变压精馏分离丙酮和环己烷的动态特性

基于丙酮-环己烷共沸体系的压力敏感性，利用Aspen Plus软件，以年度总费用(TAC)最小为目标函数对常规、部分及完全热集成变压精馏工艺进行稳态模拟与优化，并以经济最优的完全热集成变压精馏工艺为基础，借助Aspen Plus Dynamics软件建立多种不同控制结构，通过改变进料流量和进料组成考察了控制结构的有效性，并提出塔底热负荷/进料量比例控制与组成-温度串级控制相结合的改进控制结构。稳态模拟与优化结果表明，常规、部分和完全热集成三种工艺的最小TAC分别为3.64×105, 2.83×105, 2.76×105 $/y，经济最优工艺为完全热集成变压精馏。动态响应结果表明固定回流量/进料量控制结构在响应时间方面优于固定回流比控制结构，但产品纯度未达到设计值99.9wt%；而塔底热负荷/进料量比例控制与组成-温度串级控制相结合的改进控制结构能够有效保证产品纯度在99.9wt%及以上。     

Decentralized control of a kinetically controlled ideal reactive distillation column

Two-point and three-point temperature control structures are proposed for a kinetically controlled ideal reactive distillation (RD) column. The control structures maintain stable column operation for large throughput changes. However, large deviations in the final product purities are seen with three-point control giving comparatively lower deviations. The large product purity deviations are due to the kinetic regime so that two temperature set-points are adjusted in a cascade arrangement to maintain the distillate and bottoms purity. The proposed two-point and three-point structures with cascade compensation of the temperature set-points effectively maintain the distillate and bottoms purity for a large throughput decrease. However, the two-point structures fail for a large throughput increase. This is because in the kinetically controlled regime, maintaining the distillate purity requires an increase in the effective reflux ratio to internally recycle the escaping reactants back into the reactive zone. The two-point structures that use the fixed reflux ratio policy thus fail as an infeasible steady state is sought. The three-point structures effectively maintain the product purities as the reflux ratio is indirectly adjusted through the manipulation of the reflux rate. The work highlights the need for understanding the interaction between the reaction and separation sections for effective RD control system design.     

反应精馏隔壁塔生产乙酸正丁酯的优化与控制

对反应精馏隔壁塔生产乙酸正丁酯过程进行了模拟、优化与控制的系统研究。利用Aspen Plus软件模拟乙酸甲酯与正丁醇的酯交换反应过程,以年总费用（TAC）为目标函数进行过程优化,通过稳态敏感性分析及相对增益矩阵（RGA）判据得到不同的操纵变量与控制变量匹配关系,以此为基础,在Aspen Dynamics平台建立了若干控制结构并进行分析对比。结果表明,利用两股反应物呈比例进料可较为有效地抵抗进料扰动,最后提出的无再沸器热负荷与混合物进料量比值（Q_r/F）控制的改进控制结构CS3,在降低反应精馏隔壁塔控制过程超调量方面有较大的优越性。     

离子液体反应萃取精馏合成乙酸乙酯

采用离子液体1-磺酸丁基-3-甲基咪唑硫酸氢盐([HSO₃bmim][HSO₄])和1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐([BMIM][Tf₂N])分别作为催化剂和萃取剂,对乙酸甲酯与乙醇合成乙酸乙酯和甲醇的反应萃取精馏(RED)过程进行了模拟计算。在反应动力学和汽液相平衡分析基础上建立了反应萃取精馏流程,研究了理论板数、回流比、持液量、进料位置、溶剂比(萃取剂进料与原料进料摩尔流量的比值)、催化剂进料流量等参数对反应萃取精馏过程的影响。在优化的操作条件下,甲醇纯度为0.9922,乙酸乙酯纯度为0.9905,乙酸甲酯转化率为0.9922。     

Process intensification and energy saving of reactive distillation for production of ester compounds

Reactive distillation(RD) process is an innovative hybrid process combining reaction with distillation, which has recently come into sharp focus as a successful case of process intensification. Considered as the most representative case of process intensification, it has been applied for many productions, especially for production of ester compounds. However, such problems existing in the RD system for ester productions are still hard to solve,as the removal of the water which comes from the esterification, and the separation of the azeotropes of ester–alcohol(–water). Many methods have been studying on the process to solve the problems resulting in further intensification and energy saving. In this paper, azeotropic–reactive distillation or entrainer enhanced reactive distillation(ERD) process, reactive extractive distillation(RED) process, the method of co-production in RD process, pressure-swing reactive distillation(PSRD) process, reactive distillation–pervaporation coupled process(RD–PV), are introduced to solve the problems above, so the product(s) can be separated efficiently and the chemical equilibrium can be shifted. Dividing-wall column(DWC) structure and novel methods of loading catalyst are also introduced as the measures to intensify the process and save energy.     

Comparative control study of ideal and methyl acetate reactive distillation

The control of an ideal reactive distillation column is compared with that of a similar, but somewhat different, real chemical system, the production of methyl acetate. Similarities and differences are observed. Three control structures are evaluated for both systems. A control structure with one internal composition controller and one temperature controller provides effective control of both systems for both high and moderate conversion designs. A two-temperature control structure is effective when the system is overdesigned in terms of number of reactive trays, holdup and/or catalyst load. Direct control of product purity for the high-conversion/high-purity design is difficult because of system nonlinearity and interaction. Tray temperature control avoids the nonlinearity problem.     

Design of process and control scheme for cyclohexanol production from cyclohexene using reactive distillation

Cyclohexanol is a commonly used organic compound. Currently, the most promising industrial process for synthesizing cyclohexanol, by cyclohexene hydration, suffers from a low conversion rate and difficult separation. In this paper, a three-column process for catalytic distillation applicable in the hydration of cyclohexene to cyclohexanol was established to solve these. Simulation with Aspen Plus shows that the process has good advantages, the conversion of cyclohexene reached 99.3%, and the product purity was ≥99.2%. The stable operation of the distillation system requires a good control scheme. The design of the control scheme is very important. However, at present, the reactive distillation process for cyclohexene hydration is under investigation experimentally and by steady-state simulation. Therefore, three different plant-wide control schemes were established (CS1, CS2, CS3) and the position of temperature sensitive stage was selected by using sensitivity analysis method and singular value decomposition method. The Tyreus-Luyben empirical tuning method was used to tune the controller parameters. Finally, Aspen Dynamics simulation software was used to evaluate the performance of the three control schemes. By introducing ΔF ±20% and x_ENE ±5%, comparison the changes in product purity and yield of the three different control schemes. By comparison, we can see that the control scheme CS3 has the best performance.     

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.     

苯氯化侧反应精馏过程的系统设计与控制(英文)

The distillation column with side reactors (SRC) can overcome the temperature/pressure mismatch in the traditional reactive distillation, the column operates at temperature/pressure favorable for vapor-liquid separation, while the reactors operate at temperatures/pressures favorable for reaction kinetics. According to the smooth operation and automatic control problem of the distillation column with side reactors (SRC), the design, simulation calculation and dynamic control of the SCR process for chlorobenzene production are discussed in the paper. Firstly, the mechanism models, the integrated structure optimal design and process simulation systems are established, respectively. And then multivariable control schemes are designed, the controllability of SRC process based on the optimal steady-state integrated structure is explored. The dynamic response performances of closed-loop system against several disturbances are discussed to verify the effectiveness of control schemes for the SRC process. The simulating results show that the control structure using conventional control strategies can effectively overcome feeding disturbances in a specific range.     

Design and control of butyl acrylate reactive distillation column system

In this study, the design and control of a reactive distillation column system for the production of butyl acrylate has been investigated. The proposed design is quite simple including only one reactive distillation column and an overhead decanter. The optimal design is selected based on the minimization of total annual cost (TAC) for the overall system. At this optimized flowsheet condition, output multiplicity was found with reboiler duty or feed ratio as the bifurcation parameter. The highest purity stable steady state was selected as the base case condition for the control study. The overall control of this system can be achieved with no on-line composition measurements. Simple single-point tray temperature control loop is designed to infer final product purity. From results of dynamic simulation, the proposed control strategy performs very well in rejecting various disturbances while maintaining butyl acrylate product at high purity. One of the important finding in this paper is that it is better to operate this reactive distillation column not at the exact feed stoichiometric balance point for better operability reason. The control performances of the proposed operating point and the operating condition right at the exact stoichiometric balance point will be compared.     

乳酸提纯新工艺动态建模仿真和控制系统设计

基于非平衡级和拟均相假设,建立了乳酸提纯反应精馏新工艺实验装置的动态机理模型.通过改进的数值计算方法提高了模型的求解效率,设计并实现了包含物性估算系统的模型仿真平台,以促进新工艺的工业化应用.利用仿真平台对新工艺装置进行了动态特性分析,在此基础上设计了两种单端质量控制方案:直接物料平衡和间接物料平衡方案.在不同类型和幅度的过程扰动下,分析比较了两种控制方案的调节性能.结果表明直接物料平衡方案控制品质优于间接物料平衡方案,可在不同扰动情况下满足过程的产品质量和转化率的联合控制要求.非平衡级动态机理模型能够反映反应精馏过程的动态特性,分析发现反应精馏过程有着独特的过程特性,基于机理模型的仿真平台是分析反应精馏特性的有效工具.     

Design,optimization, and control of reactive distillation column for the synthesis of tert-amyl ethyl ether

The temperature–composition cascade strategy was proposed to control the reactive distillation (RD) process for the synthesis of tert-amyl ethyl ether. Aspen Split tool was adopted to obtain the design parameters of the column from the viewpoint of separating tert-amyl alcohol, ethanol, and water. The proposed procedure which included optimization and sensitivity analysis was implemented to optimize the design parameters of the column and obtain the sensitive variables simultaneously, without requirement to run various simulations. In those optimized conditions, the proposed control strategy was introduced to manage the RD process by changing the sensitive variables. From results of the dynamic simulation, it can be known that the proposed strategy was able to handle disturbances while maintain the tert-amyl ethyl ether product purity and quickly reach the steady state. Therefore, the proposed control strategy was regarded as the effective control structure and could successfully control this RD system.     

不同热集成变压精馏工艺分离乙酸乙酯/正己烷共沸物的优化与控制

基于变压精馏分离乙酸乙酯/正己烷共沸体系两塔的温差,利用Aspen Plus软件,以年度总成本最小为目标函数,对部分及完全热集成变压精馏工艺进行了稳态模拟及优化。在此基础上,利用Aspen Dynamics软件开发了多种控制结构,通过引入不同进料流量及组成的扰动测试控制结构的有效性。结果表明,完全热集成变压精馏工艺比部分热集成变压精馏工艺的经济性稍好。动态响应结果表明,部分热集成变压精馏工艺的压力?补偿温度控制结构可有效处理不同程度的干扰,能有效提高控制结构对干扰的响应速度,缩短达到新稳态的时间,保证乙酸乙酯和正己烷产品纯度在99.9wt%之上;而完全热集成变压精馏工艺的组分?温度串级控制结构仅能处理较小的组分和流量干扰,实现稳健控制,无法处理较大的干扰。综合比较两种工艺的经济性和可控性,认为部分热集成变压精馏工艺分离乙酸乙酯/正己烷共沸体系优于完全热集成变压精馏工艺。