加盐萃取精馏法制无水异丙醇过程模拟

对加盐萃取精馏法制备无水异丙醇过程进行了模拟计算,采用有序双液程(NRTL)模型对异丙醇-水-乙二醇-醋酸钾体系异丙醇-水气液平衡数据进行了回归,得到了该条件下的NRTL交互作用参数,在此基础上采用Aspen软件进行模拟计算;对理论塔板数、回流比(质量比)与进料位置进行了优化,模拟结果与现场数据吻合较好,说明采用的方法适用于加盐萃取精馏过程的模拟。     

Pressure relief of nonideal mixtures: Composition trajectories and residue curve maps

During the course of a pressure relief discharge from a vessel containing a multicomponent liquid mixture, composition changes occur that affect the properties of the vessel contents. In this work, a model of the dynamic relief process for ternary, nonideal, homogeneous mixtures is developed, under the assumption of vapor-only venting. Opening/reclosing of the relief valve introduces state-events, which require reinitialization of the model at each state transition. The relationship between the pressure relief model and the concept of residue curves, which describe simple-distillation processes, is demonstrated. It is known that the presence of azeotropes and distillation boundaries in mixtures restricts the composition trajectories of simple-distillation processes, as well as continuous distillation columns at total reflux. In this work, the residue-curve analogy is extended to vapor-only pressure-relief, where vapor composition changes directly affect the operation of the pressure-relief device. Examples of dynamic relief processes are developed for ternary mixtures with varying nonideality.     

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。     

间歇共沸精馏分离乙二醇单甲醚-水物系

通过绘制乙二醇单甲醚-水-共沸剂的简捷剩余曲线,提出了以乙酸异丙酯作为间歇共沸精馏法分离乙二醇单甲醚-水物系的共沸剂。然后完成剩余曲线数据的测定实验,根据实验数据绘制乙二醇单甲醚-水-乙酸异丙酯三元物系的剩余曲线图,确定了乙二醇单甲醚-水共沸物系的分离工艺。并通过实验研究了共沸剂加入量对乙二醇单甲醚回收率的影响,从而确定了适宜的共沸剂配比：当共沸剂与原料中水的质量比为2～2.5时,乙二醇单甲醚的一次性收率在90%以上。     

Simulation of Multicomponent Distillation Using a Nonequilibrium Stage Model

Abstract

A nonequilibrium stage model is used to predict composition profiles for binary and multicomponent distillation in a column of spheres and cylinders with a known interfacial area. The profiles generated by the model are compared with experimental data for the binary systems methanol—isopropanol, methanol—water, and isopropanol—water, and for the ternary systems methanol—isopropanol—water and acetone—n—hexane—cyclohexane. The model predicts with a high accuracy the experimental data with an average deviation lower than 1 mol%.     

Method and Apparatus for Precision In‐Line Sampling of Distillate

Abstract

In this short note we present a method and describe a simple apparatus for use with simple, fractional, and steam distillation operations in which the operator requires a precise measurement of instantaneous distillate composition as the distillation proceeds. There are many examples in which such a measurement will play a critical role. One such example is in the measurement of boiling or distillation curves, where one desires an explicit measure of distillation process temperatures as a function of distillate volume fraction. The ability to augment temperature‐volume distillation curves with composition information is very helpful. The optimization of critical distillation conditions for the separation of sensitive solutes is another example in which instantaneous distillate composition is of value. The purification of reactants before a reaction is still another example. In all of these cases, it is the instantaneous composition that emerges from the condenser that is needed, rather than the integrated composition of the distillate that accumulates in the receiver. In this note, the apparatus and method are described, and an example is given with a mixture of n‐decane/n‐tetradecane.     

DMC-甲醇-水三元混合物的萃取精馏分离工艺

运用Aspen Plus软件回归文献数据校正了碳酸二甲酯（DMC）-水（H₂O）混合物的UNIQUAC热力学模型参数,并以该模型为基础分析了水作为萃取剂萃取精馏分离DMC-甲醇（CH₃OH）-水三元混合物的分离原理,结合混合组分的三角相图和物料组成设计了反向萃取精馏工艺,发现选用水为萃取剂可以利用DMC-水的部分互溶特性,通过三塔精馏即可分离DMC-甲醇-水三元混合物,沸点较高的DMC和少量水由塔顶馏出,而沸点较低的甲醇和大部分水由塔底采出,避免了DMC-甲醇二元共沸物的形成。同时,在相同分离要求下设计了变压精馏工艺,通过对两个精馏工艺参数模拟优化,发现萃取精馏工艺的总冷凝负荷和总加热负荷分别为888.7kW和898.2kW,其总能耗较变压精馏工艺节约了47.2%,萃取精馏工艺的年总费用（TAC）比变压精馏工艺下降了48.8%。     

Separation of aqueous isopropanol by reactive extractive distillation

A new separation method of reactive extractive distillation is proposed for the separation of isopropanol and water, using the mixture of ethylene glycol (C₂H₆O₂) and glycollic potassium (C₂H₅O₂K) as an entrainer. Vapor–liquid‐equilibrium (VLE) measurements confirmed that the entrainer was effective for this separation. Using a feed/solvent volume ratio of 1:1, isopropanol with a concentration over 96.0% weight fraction was obtained by the reactive extractive distillation process and the azeotropic point was eliminated. A novel process of separating isopropanol and water is designed on the basis of reactive extractive distillation to obtain the product with different concentrations, which may have a lasting value in industry. © 2002 Society of Chemical Industry     

Simulation and optimization of extractive distillation sequence with pre-separator for the ethanol dehydration using n-butyl propionate

Extractive distillation is the most promising alternative for the ethanol-water separation than azeotropic and pressure swing distillation using suitable solvent n-Butyl propionate. We have studied, simulated, optimized and economically evaluated the separation of a mixture of 50 mole% ethanol and 50 mole% water to treat the 16 Kmol/hr (512.67 kg/hr) of the original mixture. Rigorous simulation and optimization has been carried out by means of a software CHEMCAD version 6.5 using thermodynamic model UNIQUAC with binary interaction parameters. The simulations allow us to conclude that extractive distillation is more economical and trustworthy than pressure swing distillation due to the relative pressure insensitive nature of the ethanol-water mixture after the azeotropic composition. The separation of 99.7% of ethanol from ethanol water mixture claim by Mulia-Soto, Flores-Tlacuahuac, 2011 is contradictory as the feasibility for the operating pressure of 10 atm with or without heat integration.     

An experimental simulation of distillation column concentration profiles using a batch apparatus

There has been a growing interest in the use of residue curves for the preliminary design and sequencing of distillation columns. Residue curves are used not only to predict composition changes in separation processes, but also to determine the feasibility of proposed separations, and flowsheet development (Chem. Eng. Sci. 33 (1977) 281).An experimental technique has been developed for the measurement of these residue curves. (Distillation & absorption ’97, Inst. Chem. Eng. 1 (1997) 187). It can be shown that the time-dependent composition profiles obtained in a modified form of this apparatus are mathematically equivalent to the position-dependent profiles in a continuous distillation column. Hence, it is possible to experimentally simulate a distillation column profile in a small batch apparatus using only small quantities of material.The modified apparatus consists of a still immersed in a heated oil bath so that a liquid feed is continuously supplied to the still. Samples of liquid are then analysed over time using a gas chromatograph. The results from an experimental system have been compared to available information and simulations to determine the accuracy of the apparatus.This technique has several advantages over working with distillation columns, firstly in the sample size required, and secondly in the ease of operation. The method allows quick and low-cost measurements of the concentration variables that model a distillation column. The information obtained this way could prove useful for the selection of feasible systems and for finding minimum reflux requirements. It could also be very valuable for screening of complex systems where only small amounts of material are available and simulations may be very difficult.     

异丙醇-环己烷废液的提纯

对大学物理化学实验中的“双液系气-液平衡相图的绘制”实验产生的异丙醇-环己烷废液进行了分离提纯。先以水为萃取剂,对异丙醇-环己烷混合物进行萃取分离,再分别精馏提纯,得到纯度为99．492％的环己烷和纯度为98．710％的异丙醇。     

异丙醇-环己烷萃取精馏过程模拟与优化

利用化工流程模拟软件Aspen Plus对异丙醇-环己烷共沸物系的双塔连续萃取精馏过程进行了模拟计算与优化。首先根据溶剂相似相溶原理,先初选出糠醛和硝基苯作为备选溶剂,再通过汽液平衡试验及ChemCAD模拟筛选,确定糠醛为最适宜溶剂,选择NRTL模型作为物性方法,使用RadFrac模块进行模拟计算,并利用灵敏度分析模块对各工艺参数进行优化。结果表明,最适宜工艺方案为：萃取精馏塔理论塔板数为30,原料在第26块板进料,溶剂在第12块板进料,物质的量回流比为1.8,溶剂质量比为3∶1;溶剂回收塔理论板数为15,进料位置在第10块板,物质的量回流比为1.0。分离效果可达到环己烷质量分数为99.74%,异丙醇质量分数为99.61%。模拟和优化结果为分离过程的优化操作和设计提供了依据。     

Synthesis of cylohexanol by three-phase reactive distillation: influence of kinetics on phase equilibria

A reactive distillation process is being suggested for the production of the commercially interesting intermediate cyclohexanol from cyclohexene and water, which avoids some of the drawbacks of the conventional liquid-phase cyclohexane oxidation process, especially with respect to operational safety. This reactive distillation process has its own intricate challenges due to the fact that reaction, distillative separation and liquid-phase splitting occur simultaneously. The interaction of these three phenomena is studied using residue curve maps for both, model simulations and experimental data. Based on the fixed point analysis of the residue curves, a novel process is proposed for the reactive separation of cyclohexene/cyclohexane mixtures which is difficult to be carried out by conventional distillation due to very close boiling temperatures.     

简单蒸馏残余曲线图结构的研究

介绍了三组元混合物共沸系统中简单蒸馏残余曲线图结构的性质和画法。此画法只需知道纯组分和共沸物的沸点及相应组成即可。大多数情况下 ,此画法能唯一确定残余曲线图 ,并且还能够检验沸点温度数据的正确性     

萃取精馏分离异丙醇-水共沸体系的模拟与优化

对异丙醇-水共沸体系的萃取精馏过程进行模拟与优化。以乙二醇为萃取剂,基于UNIFAC模型,使用Aspen Plus化工模拟软件中的RadFrac模块进行萃取精馏模拟,并利用灵敏度分析模块对各工艺参数进行灵敏度分析与优化。结果表明,以乙二醇做萃取剂分离异丙醇-水共沸体系是可行的。对于处理流量5000kg·h-1的异丙醇-水共沸溶液,精馏塔具有22块塔板时,原料进料位置在第16块塔板,萃取液进料位置在第3块塔板,摩尔回流比为1.4,萃取剂与原料的进料比为2∶1,塔顶异丙醇质量分数可达0.9981,萃取精馏塔的分离效果和热负荷达到最优。模拟和优化的结果对工业化设计和生产具备指导意义。     

Prediction of Optimum Composition of the Mixed Solvent N-Methylpyrrolidone/Ethylene Glycol for the Extraction of Aromatics

Abstract

The optimum composition of mixed solvent which is usually determined experimentally is predicted by a method in which the minimum total energy required for extraction and subsequent solvent recovery by distillation is calculated. The method is demonstrated using N-methylpyrrolidone (NMP) and monoethylene glycol (EG) as mixed solvent for the extraction of benzene from a hexane/benzene mixture. UNIFAC method was used to predict liquid phase equilibria in extraction and liquid-vapor equilibria in distillation. To demonstrate the method flexibility, ethylene glycol was replaced by water as another alternative solvent, and the optimum composition of the new mixed solvent of NMP/water was predicted. However this particular mixed solvent required much higher energy than NMP/EG case.     

离子液体萃取精馏制取乙醇的计算机过程模拟与优化

采用乙醇-水-1,3-二甲基咪唑二甲酯磷酸盐（[MMIM]+[DMP]?）体系的汽液相平衡数据回归了NRTL模型的二元交互参数。根据对剩余曲线的分析确定选用[MMIM]+[DMP]?作为萃取剂进行萃取精馏方案的可行性。通过模拟计算得到最佳操作条件：萃取剂进料量为30～40 kg/h,回流比为0.6,原料进料位置为第23块理论板,萃取剂进料位置为第2块理论板,此时塔顶产品浓度可达到99.6%。通过模拟确定的[MMIM]+[DMP]?用于乙醇-水萃取精馏的设计及操作参数为实验研究提供了数据基础,为离子液体工业化的研究提供了理论基础。     

Representation of Adsorption Data for the Isopropanol‐Water System using Neural Network Techniques

Molecular sieves and palm stone, a newly developed bio‐based adsorbent, were used to break an azeotropic isopropanol‐water system via an adsorptive distillation process. Equilibrium data at different inlet water contents are presented. The data were obtained with a fixed bed adsorptive distillation process using Type 3A and Type 4A molecular sieves and palm stone. An artificial neural network (ANN) technique was used to represent the isotherm equilibrium data of this azeotropic system. The ANN prediction results were compared with the Guggenheim‐Anderson‐de Boer (GAB) isotherm model. It was possible to break the isopropanol‐water azeotrope using this separation process with the adsorbents used in this work. Water uptake increases as the water content in the feed decreases from 16 % to 10 %. Although the GAB isotherm model was found to be applicable to the water vapor sorption data on the adsorbents examined, the ANN model fitted the equilibrium data more efficiently.     

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.     

反应精馏过程图解法设计策略研究

从反应精馏过程图解法设计的理论研究出发,探讨了反应空间、转换组成变量以及剩余曲线等应用范围和局限性;通过分析反应精馏操作线方程的变化,提出了图解法设计反应精馏过程的策略;（1）用奇异点判断法结合实验数据可判定应用反应精馏过程的可行性;（2）借助反应空间可判断该过程能否在单塔中得到完全分离;（3）图解法设计的多种设计结果及相应对策。采用实例验证了该策略的可行性。