REDUCING STATIC DEVIATIONS OF PRODUCT QUALITIES IN THE TEMPERATURE CONTROL OF AN IDEAL HEAT-INTEGRATED DISTILLATION COLUMN

Two strategies are proposed in this work for the reduction of static deviations of product qualities in the dual-point temperature control of a simulated ideal heat-integrated distillation column. The key to achieve this purpose is to sense the changes in operating conditions and make appropriate adjustments simultaneously to the set-points of the top and bottom control loops. The first method is based on the inferential signals extracted from the composition of products and the second one from the temperatures of the top and bottom stages. Both strategies are intensively studied through the operation of the simulated ideal heat-integrated distillation column separating a binary equimolar mixture of benzene and toluene, and it is found that they could work effectively to decrease the static deviations in product qualities. The strategies are characterized by great simplicity in principle and a relatively small effort in process modeling, thereby allowing wide applications in the operation of various distillation columns with a dual-point temperature control scheme.     

Enhanced temperature difference control of distillation columns based on the averaged absolute variation magnitude

Temperature difference control (TDC) schemes can clearly suppress the adverse influence of pressure variations on product quality control of various distillation columns (DCs) by employing temperature differences (TDs) between the sensitive stage temperature (T_S) and reference stage temperature (T_R), i.e., T_S-T_R, to infer the controlled product qualities. However, because the TDC scheme has failed to specially take the corresponding relationship between the TD employed in each control loop and the controlled product quality into account, it may suffer from relatively large steady-state errors in the controlled product qualities. To address this problem, an enhanced TDC (ETDC) scheme is proposed in the current article, in which an enhanced TD (ETD), i.e., T_S-α×T_R, is employed to replace the conventional TD for each control loop. While the locations of the sensitive and reference stages of the ETD are respectively determined according to sensitivity analysis and SVD analysis, the adjusted coefficient α is set to be the ratio between the averaged absolute variation magnitudes (AAVMs) of the T_S and T_R so that the relationship between the T_S and T_R can be appropriately coordinated. With reference to the operations of three different distillation systems, i.e., one conventional DC distilling an ethanol (E)/butanol (B) binary mixture, one conventional DC distilling an E/propanol (P)/B ternary mixture, and one dividing-wall distillation column distilling an E/P/B ternary mixture, the performance of the ETDC scheme is assessed by compared with the conventional TDC scheme and the double TD control (DTDC) scheme. The dynamic simulation results show that the ETDC scheme is better than the conventional TDC scheme with reduced steady-state errors in the controlled product qualities and improved dynamic responses, and is comparable with the DTDC scheme despite the less temperature measurements are employed.     

外部环流反应精馏塔的分散控制方案设计

对于具有最不利相对挥发度排序（即反应物为最轻和最重组分，生成物为中间组分）的四元反应分离物系而言，在反应精馏塔的顶部和底部之间引入外部环流能够提高系统的反应分离效率，从而大幅度地降低系统的能量消耗和固定投资成本。以理想四元可逆放热反应的分离为例，研究了外部环流反应精馏塔的分散控制方案的设计问题。结果表明外部环流的引入提高了系统的反应速率，使得外部环流反应精馏塔的闭环控制效果更好（与传统反应精馏塔相比），对干扰的处理能力更强。另外，由于外部环流反应精馏塔比常规反应精馏塔有更多的操作变量（即外部环流流量），利用该变量对出料浓度进行控制，可以进一步提高系统的闭环控制效果。     

Nonlinear model based control of two-product reactive distillation column

Nonlinear feedback control scheme for reactive distillation column has been proposed. The proposed control scheme is derived in the framework of Nonlinear Internal Model Control. The product compositions and liquid and vapor flow rates in sections of the reactive distillation column are estimated from selected tray temperature measurements by an observer. The control scheme is applied to an example reactive distillation column in which two products are produced in a single column and the reversible reaction A+B=C+D occurs. The relative volatilities are favorable for reactive distillation so that the reactants are intermediate boilers between the light product C and the heavy product D. Ideal physical properties, kinetics, and vapor-liquid equilibrium are also assumed. It is shown that the proposed control scheme keeps tight product composition control.     

简化外部热耦合双精馏塔的控制与优化

针对具有3个换热器结构的外部热耦合双精馏塔(S-EHIDDiC),提出了一种新型的控制与优化策略。顶部与底部换热器的热负荷能够改变高压精馏塔的回流量和低压精馏塔的上升汽量,因而可以用来控制高压精馏塔塔顶和低压精馏塔塔底的产品质量。这种控制方法与常规精馏塔的LV控制结构相似。S-EHIDDiC还有多余的决策变量(如进料分流比,高压精馏塔塔压和中间换热器的热负荷),可以对稳态操作进行优化。闭环仿真证明了这种控制结构的可行性,稳态优化也提高了系统的热力学效率。     

Enhancing mass and energy integration by external recycle in reactive distillation columns

The synthesis and design of reactive distillation columns separating reacting mixtures with the most unfavorable relative volatilities (i.e., the reactants are the heaviest and lightest components with the products being the intermediate ones) are described. The unfavorable thermodynamics poses great difficulties in combining the reaction operation and the separation operation involved and limits severely the potential of reactive distillation columns in the reduction of capital investment (CI) and operating cost. To remove the limitation, we propose two strategies for facilitating the synthesis and design of this kind of reactive distillation columns in this article. One is to arrange prudentially the reactive section so as to strengthen internal energy integration between the reaction operation and the separation operation involved; that is, while the reactive section should be placed at the bottom of the reactive distillation columns separating exothermic reactions, it should be at the top of the reactive distillation columns separating endothermic reactions. The other is to introduce an external recycle flow between the two ends of the reactive distillation columns to reinforce internal mass integration and internal energy integration between the reaction operation and the separation operation involved; that is, whereas the external recycle flow should be directed from the top to bottom of the reactive distillation columns separating exothermic reactions, it should be from the bottom to top of the reactive distillation columns separating endothermic reactions. Separation of four hypothetical ideal (i.e., two quaternary and two ternary systems, respectively) and two real nonideal (i.e., two quaternary systems) reacting mixtures is chosen to evaluate the proposed strategies. The results show that they can considerably lower energy requirement besides a further reduction in CI. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2015–2032, 2013     

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。     

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.     

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.     

Design and Control of Extraction Distillation for Dehydration of Tetrahydrofuran

Design and control of an extractive distillation system for tetrahydrofuran (THF) dehydration with ethylene glycol as entrainer is investigated. The main module is a two‐column system containing an extractive distillation column, whose top stream is the desired product THF, and an entrainer recovery column. Economic analysis with total annual cost as the objective function is developed. Two kinds of control strategies are explored for THF dehydration. The responses reveal that the control structure with fixed reflux ratio cannot maintain the bottom liquid level of the entrainer recovery column, while the control scheme with fixed reboiler heat duty/feed flow ratio exhibits good control performance in spite of large deviations in feed flow rate and feed composition.     

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.     

Unique influences of reboiler inventory control on the operation of totally reboiled reactive distillation columns

In this work,the dynamics and operation of the totally reboiled reactive distillation columns are visualized in terms of transfer function based process models.This kind of processes is found to be characterized by underdamped step responses due to the special topological configuration and the intricate interplay between the reaction operation and the separation operation involved.The under-dampness can be substantially alleviated through the tight inventory control of bottom reboiler and this presents beneficial effects to process dynamics and operation.Two totally reboiled reactive distillation columns,separating,respectively,a hypothetical synthesis reaction from reactants A and B to product C,and a real decomposition reaction from 1,4-butanediol to tetrahydrofuran and water,are employed to demonstrate these uncommon behaviors.The results obtained give full support to the above qualitative interpretation.Despite the strong influences of reaction kinetics and thermodynamic properties of the reacting mixtures,the totally reboiled reactive distillation columns am generally considered to present such unique behaviors and require tight inventory control of bottom reboiler to facilitate their control system development.     

The use of dilute acetic acid for butyl acetate production in a reactive distillation: Simulation and control studies

The recovery of dilute acetic acid, which is widely found as a by-product in many chemical and petrochemical industries, becomes an important issue due to economic and environmental awareness. In general, separation of acetic acid in aqueous solution by conventional distillation columns is difficult, requiring a column with many stages and high energy consumption. As a result, the primary concern of the present study is the application of reactive distillation as a potential alternative method to recover dilute acetic acid. The direct use of dilute acetic acid as reactant for esterification with butanol to produce butyl acetate in the reactive distillation is investigated. Simulation studies are performed in order to investigate effect of the concentration of dilute acetic acid and key process parameters on the performance of the reactive distillation in terms of acetic acid conversion and butyl acetate production. In addition, three alternative control strategies are studied for the closed loop control of the reactive distillation. The control objective is to maintain the butyl acetate in a bottom product stream at the desired purity of 99.5 wt%.     

Singular reactive flash dynamics

Reactive flash is commonly used as a toy model for understanding the dynamics of industrial reactive distillation processes. Reactive distillation can display complex bifurcation phenomena, including multiplicities and Hopf oscillations. In principle, the simplicity of reactive flash might provide important insights for the design, operation and control of reactive distillation processes. Recent studies have shown that steady state multiplicity and Hopf phenomena can be present even in reactive flash, and such bifurcations are the product of the interaction of the vapor–liquid separation with the chemical transformation. This work uses a simple reactive flash model to show that reactive flash can display singular dynamics represented by spontaneous transitions from one-phase (liquid) to two-phase (liquid-phase) operating modes. Different steady state operating scenarios are described, including a globally stable flashing to unfeasible operation leading to emptiness of the liquid phase. The results are discussed in terms of potential implications for the operation and control of reactive distillation columns.     

离子液体催化反应精馏合成乙酸乙酯工艺模拟

为研究离子液体在反应精馏中的作用,采用离子液体1-丁基-3-甲基咪唑硫酸氢盐（[BMIM]HSO₄）作为催化剂,对乙酸和乙醇合成乙酸乙酯的反应精馏流程进行了计算模拟。在确定了参数的酯化反应动力学的基础上,用Aspen Plus软件建立了反应精馏流程,研究了催化剂用量、精馏段理论板数、反应段理论板数、乙醇进料位置、进料摩尔比、持液量及回流比等参数对反应精馏过程的影响。研究结果表明,塔顶乙酸乙酯的质量分数随催化剂用量、精馏段理论板数、反应段理论板数和持液量增大而增大,工艺流程存在最佳回流比以及最佳进料酸醇摩尔比。得到的优化条件如下：离子液体与乙酸摩尔比为1：2.5,进料酸醇摩尔比为4：1,理论塔板数为21块,乙酸和催化剂在第7块理论塔板进料,乙醇在第19块理论塔板进料,塔板持液量0.1L,回流比为4,塔顶乙酸乙酯的质量分数可以达到98.73%。     

考虑不同产品选择性目标的乙醇胺反应精馏塔模拟与优化

提出以环氧乙烷和液氨为原料,水为催化剂,反应精馏塔合成乙醇胺的工艺。分别以一乙醇胺（MEA）和二乙醇胺（DEA）的选择性最大为目标,探讨了在同一反应精馏塔中实现不同产物选择性目标的可行性和可达到的最大选择性。研究在Aspen Plus模拟软件上进行,通过考察操作压力、水进料量、进料氨烷比、再沸比、环氧乙烷进料位置等参数对反应精馏的影响规律,取得实现不同产物选择性目标的参数优化调节方法。研究表明,大的氨烷比、水进料量和再沸比有利于提高MEA选择性,小的氨烷比、水进料量和再沸比则有利于提高DEA选择性,在优化条件下,MEA选择性可达70.30%,DEA选择性可达41.89%。与文献方法比较,采用反应精馏合成乙醇胺具有明显的优越性和操作柔性。     

Process alternatives for methyl acetate conversion using reactive distillation. 1. Hydrolysis

In a polyvinyl alcohol (PVA) plant, reaction stoichiometry indicates that equal molar of methyl acetate is generated for every mole of PVA produced. This work explores an alternative to convert methyl acetate back to acetic acid (raw materials of PVA plant), methyl acetate (MeAc) hydrolysis. The design and control of methyl acetate hydrolysis using reactive distillation is studied. Because of the small chemical equilibrium constant (∼0.013) and unfavorable boiling point ranking (MeAc being the lightest boiler), the reactive distillation exhibits the following characteristics: (1) total reflux operation and (2) excess reactant (water) design. The proposed flowsheet consists of one reactive distillation column with a reactive reflux drum, two separation columns, and one water-rich recycle stream. A systematic design procedure is used to generate the flowsheet based on the total annual cost (TAC). Two dominate design variables are: recycle flow rate (for the degree of excess in water) and the overhead impurity level of acetic acid in the product column (to avoid tangent pinch). Finally, the operability of the hydrolysis plant is evaluated. A plantwide control structure is developed followed by process identification and controller tuning. The results show that reasonable control performance can be achieved using simple temperature control for feed flow and feed composition disturbances.     

减压反应蒸馏去除热镀锌FeCl2污泥中的Cl-

由于Cl^-对植物的生长具有很高的“氯毒害”,而热镀锌FeCl₂污泥中Cl^-的含量极高,因此不能直接作为一般废物最终处置。采用减压反应蒸馏去除FeCl₂污泥中的Cl^-,由于FeCl₂水解生成的HCl被减压蒸馏带出、Fe（OH）₂在空气曝气作用下氧化成Fe（OH）₃,经过滤干燥后形成水合氧化铁（Fe₂O₃·nH₂O）。实验中首先在自制的减压反应蒸馏装置中进行3因素4水平正交实验研究,随后做单因素优化实验研究。减压反应蒸馏去除FeCl₂溶液中Cl^-的优选工艺条件：FeCl₂浓度为1.50 mol/L、加热温度为75 ℃、反应蒸馏时间为120 min,系统真空度控制在0.06 MPa,Cl^-的去除率达85.5%。将优选的工艺条件应用于热镀锌FeCl₂污泥中Cl^-的去除,其去除率可达84.0%。     

Propylene glycol and ethylene glycol recovery from aqueous solution via reactive distillation

Propylene glycol (PG) and ethylene glycol (EG) are recovered from aqueous solution via reaction with acetaldehyde to form acetals in a reactive distillation column. The reaction takes place over Amberlyst 15 cationic exchange resin catalyst, held in structured packing in the column reactive zone. Gycol solution is fed to the column at the top of the reactive zone and acetaldehyde is fed at the bottom of the reactive zone. The acetals produced, 2,4-dimethyl-1,3-dioxolane from PG and 2-methyl-1,3-dioxolane from EG, form minimum-boiling azeotropes with water and exit the top of the column along with excess acetaldehyde; residual water exits the column as the bottoms stream. In a pilot-scale column, steady-state PG conversions of over 90% are obtained. Hydrolysis of both acetals is rapid and allows complete recovery of high purity PG and EG and recycle of acetaldehyde. Simulation of PG acetalization using a kinetic rate-based model in AspenPlus process simulation software gives good agreement with experimental data using an HETP of . The proposed recovery scheme has application for PG and EG recovery from pure polyol solutions and from mixed polyol streams such as those generated in carbohydrate hydrogenolysis.     

Control of a reactive batch distillation process using an iterative learning technique

Quadratic criterion-based iterative learning control (QILC) was applied to a numerical reactive batch distillation process, in which methacrylic anhydride (MAN) is produced through the reaction of methacrylic acid with acetic anhydride. The role of distillation is to shift the equilibrium conversion toward the direction of the product by removing acetic acid (AcH), a by-product of the reaction. Two temperatures at both ends of the column were controlled by individual control loops. A nonlinear PID controller manipulating the reflux ratio was employed to regulate the top temperature at the boiling point of AcH. A constrained QILC was used for the tracking of the reactor temperature. A time-varying reference trajectory for the reactor temperature that satisfies the target conversion and purity of MAN was obtained through repeated simulations and confrimation experiments in the pilot plant. The QILC achieved satisfactory tracking in several batch runs with gentle control movements, while the PID control as a substitute of the QILC in a comparative study exhibited unacceptable performance.