A review of extractive distillation from an azeotropic phenomenon for dynamic control

Extractive distillation is an effective method for separating azeotropic or close boiling point mixtures by adding a third component. Various technologies for performing the extractive distillation process have been explored to protect the environment and save resources. This paper focuses on the improvement of these advanced technologies in recent years. Extractive distillation is retrieved and analyzed from the view of phase equilibrium, selection of solvent in extractive distillation, process design, energy conservation, and dynamic control. The quantitative structure–property relationship used in extractive distillation is discussed, and the future development of extractive distillation is proposed to determine how the solvent affects the relative volatility of the separated mixture. In the steady state design, the relationship between the curvature of the residue curve and parameters of the optimal steady state is also highlighted as another field worthy of further study to simplify the distillation process.     

非理想多组分混合物中质量传递过程基于Maxwell-Stefan扩散理论的建模及数值分析(英文)

The Intalox metal tower packing was used to simulate an industrial relevant extractive distillation column for purifying azeotropic multicomponent mixture.In order to explain the inconsistencies in the modeling of transfer process in nonideal multicomponent distillation column,a method was developed with equilibrium stage models(EQ)and non-equilibrium model(NEQ)incorporated with Maxwell-Stefan diffusion equations in the framework of AspenONE  simulator.Dortmund Modified UNIFAC(UNIFAC-DMD)thermodynamic model was employed to estimate activity coefficients.In addition,to understand the reason for the diffusion against driving force and the different results by EQ and NEQ models,explicit investigations were made on diffusion coefficients, component Murphree efficiency and mass transfer coefficients.The results provide valuable information for basic design and applications associated with extractive distillation.     

Environmental,economic and exergy analysis of separation of ternary azeotrope by variable pressure extractive distillation based on multi-objective optimization

In this work, the ternary azeotrope of tert-butyl alcohol/ethyl acetate/water is separated by extractive distillation(ED) to recover the available constituents and protect the environment. Based on the conductor like shielding model and relative volatility method, ethylene glycol was selected as the extractant in the separation process. In addition, in view of the characteristic that the relative volatility between components changes with pressure, the multi-objective optimization method based o...     

Batch Extractive Distillation in a Column with a Middle Vessel

Batch extractive distillation was studied in a column with a middle vessel. The process was simulated by a constant holdup model and solved by two point implicit method. Acetone and methanol mixture was separated in such a setup using water as solvent. The simulation agrees well with experimental results. The experimental and simulation results show that the solvent at the bottom and the product at the top of the column can be withdrawn simultaneously for a long period of time. It needs more time for the solvent to reach high purity than that required for the more volatile component to reach high purity, so that the time to withdraw solvent from the bottom is delayed.     

拟稳态模型用于间歇萃取精馏的数值模拟

Batch extractive distillation (BED) is a special method used in the distillation process by adding a solvent into the batch distillation column to alter the relative volatility of the components and improve the separation. A comprehensive design and simulation method is required due to the complexity of BED. In this study, a quasi-steady-state model for BED is proposed, the derivation and solution of the model are presented. This shortcut model can be used to simulate the composition and temperature of the reboiler, the top and other plates of the column in a batch extractive distillation operation. The calculated values are in good agreement with the experi-mental data. The results show that the quasi-steady-state model is a practical method because of some advantages such as high precision and fast calculation.     

Isobaric vapor–liquid equilibrium for binary system of aniline+methyl-N-phenyl carbamate

In this study,the quasi-static ebulliometric method was used to measure both of the vapor pressures of methyl N-phenyl carbamate(MPC),and the isobaric vapor–liquid equilibrium(VLE) data of the aniline and MPC binary system.The measured vapor pressure data of MPC,at different temperature ranging from 369.60 to 389.54 K,fitted well with the Antoine equation.The VLE data for the aniline and MPC system at(2.00,4.00,6.00,7.00 and 8.00) k Pa were correlated by both of nonrandom two-liquid(NRTL) and Wilson models.The parameters of the two models were obtained by regressing the experimental data,with the absolute temperature deviations of 0.54 K and 0.53 K,respectively.The relative volatility of the binary system calculated was all far more than 1,which gives the conclusion that the high purity MPC can be separated from aniline and MPC binary system by rectification or distillation technology.     

萃取精馏溶剂选择性的温度效应

Extractive distillation is an important and useful technique for separating close boiling and azeotropic liquid mixtures. Solvent selectivity is the key to achieving success. In this paper, the relation of solvent selectivity uersus temperature for different mixed systems (C6H6 C6H12 DMSO,C6H6 C6H12 DMF, EtOH EA DMF DMSO, C6H6 C6 H12 DMF DMSO) was examined by the modified UNIFAC model, which is a well-tested method to select a solvent for extractive distillation.With increasing temperature, solvent selectivity was decreased. In addition, the influence of temperature on solvent selectivity was set forth for the first time by using the Clausius-Mosotti equation.     

亲和胶质气体泡沫的制备及其对胰蛋白酶的吸附分离特性

Triton X-114, an non-ionic surfactant, was modified with the affinity ligand of trypsin, paminobenzamidine (PAB) and the affinity surfactant (PAB-TX) was synthesized. Then, the affinity surfactant was used to prepare affinity-based colloidal gas aphrons (CGA). The stability of the affinity CGA was investigated at different temperatures and compared with that of the CGA prepared from Triton X-114. Compared with the CGA from Triton X-114, the affinity CGA showed high selective adsorption property for trypsin. In the separation of a protein mixture, recovery yield higher than 74% were achieved for trypsin and the separation factor reached over 1.5. The results showed that the affinity CGA possessed promising selectivity for separating trypsin from a protein mixture.     

带有中间储罐的塔用于间歇萃取精馏

Batch extractive distillation was studied in a column with a middle vessel. The process was simulated by a constant holdup model and solved by two point implicit method. Acetone and methanol mixture was separated in such a setup using water as solvent. The simulation agrees well with experimental results. The experimental and simulation results show that the solvent at the bottom and the product at the top of the column can be withdrawn simultaneously for a long period of time. It needs more time for the solvent to reach high purity than that required for the more volatile component to reach high purity, so that the time to withdraw solvent from the bottom is delayed.     

Effects of imidazolium-based ionic liquids on the isobaric vapor–liquid equilibria of methanol + dimethyl carbonate azeotropic systems

The separation of methanol(MeOH) and dimethyl carbonate(DMC) is important but difficult due to the formation of an azeotropic mixture. In this work, isobaric vapor–liquid equilibrium(VLE) data for the ternary systems containing different imidazolium–based ionic liquids(ILs), i.e. MeOH + DMC + 1-butyl-3-methy-limidazolium bis[(trifluoromethyl)sulfonyl]imide([Bmim][Tf_2N]), MeOH + DMC + 1-ethyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide([Emim][Tf_2N]), and MeOH + DMC + 1-ethyl-3-methylimidazolium hexafluorophosphate([Emim][PF6])) were measured at 101.3 kPa. The mole fraction of IL was varied from0.05 to 0.20. The experimental data were correlated with the NRTL and Wilson equations, respectively. The results show that imidazolium-based ILs were beneficial to improve the relative volatility of MeOH to DMC,and [Bmim][Tf_2 N] showed a much more excellent performance on the activity coefficient of MeOH. The interaction energies of system components were calculated using Gaussian program, and the effects of cation and anion on the separation coefficient of the azeotropic system were discussed.     

萃取精馏分离甲苯和甲基噻吩中萃取溶剂的选择

在一系列萃取溶剂存在下,通过测定常压气液平衡试验数据来计算甲苯与甲基噻吩的相对挥发度,并且以相对挥发度为评价指标,考察了单一萃取剂对甲苯与甲基噻吩分离过程的影响,从而研究分离纯化由焦化苯中得到的甲苯与甲基噻吩(2-甲基噻吩和3-甲基噻吩)时所需要的萃取溶剂.结果表明:以N-甲基吡咯烷酮为萃取剂且溶剂体积比为7时,甲苯与...     

萃取精馏分离碳酸二甲酯-乙醇二元共沸物

测定了101.3 kPa下乙醇-碳酸二甲酯（DMC）和DMC-糠醛二元体系的汽液平衡数据,以及乙醇-DMC-糠醛体系在溶剂比为1∶1时的三元汽液平衡数据。结果表明,糠醛的加入可以改变乙醇和DMC的相对挥发度,并且当糠醛的摩尔分数大于0.25时,乙醇-DMC二元物系的共沸点消失。因此,可以采用萃取精馏的方法以糠醛为溶剂分离乙醇和DMC的混合物。采用Aspen Plus软件对连续萃取精馏分离乙醇-DMC共沸物的过程进行了模拟。结果表明,单塔带侧线采出的操作方式比双塔操作方式更有优势。     

从异丙醇装置副产中分离精制异丙醚的工艺研究

采用萃取精馏和共沸精馏的试验方法,进行了从异丙醇装置副产中分离精制异丙醚工艺的研究,结果可以得到纯度大于99%的异丙醚和纯度大于99.5%的异丙醇,并且产率较高。     

HFC-125与CFC-115的分离方法

研究了含五氟氯乙烷(CFC-115)的五氟乙烷(HFC-125)混合物中提纯HFC-125的方法。并用萃取精馏法将其分离提纯。萃取剂可以是环己酮、乙腈、硝基甲烷、丙酮与环己酮的混合物,乙酸乙酯与乙酸丁酯的混合物或工业乙醇和乙酸乙酯的混合物。用这些萃取剂可将CFC-115/HFC-125体系的相对挥发度提高至2.7以上。富集了HFC-125的萃取液经简单分馏即可得到精制的HFC-125。萃取剂可反复使用。采用此工艺的萃取精馏塔理论塔板数可降低至20块以下。该工艺已获中国发明专利(CN1120828C),并已在千吨级生产装置上实际应用。     

含少量水与低碳醇的异丁醇物系精馏工艺设计

共沸精馏通常加入溶剂以改变组分间相对挥发度实现分离。利用工程软件Aspen Plus模拟异丁醇-水、正丙醇-水、异丙醇-水、乙醇-水、异丁醛-水等组分常压共沸组成,模拟计算结果和文献值相符,并在三角相图上利用剩余曲线和进料点进行精馏方案设计。在给定进料条件下,对于异丁醇-水及低碳醇-水共沸物系精馏方案,不加入共沸剂亦可得到合格的塔顶、塔釜产品。     

萃取精馏复合溶剂的复配选择

提出按溶剂之间复配形成氢键的情况和修正的UNIFAC模型相结合的方法选择分离共沸体系的萃取精馏复合溶剂。准确测量了共沸体系与萃取精馏单溶剂和复合溶剂的汽液平衡数据,结果表明采用的萃取精馏单溶剂和复合溶剂的选择方法具有较好的准确度,模拟值与实验值比较,相对偏差均小于9%。通过综合比较得到分离乙酸乙酯-乙醇、乙醇-水和环己烷-苯3个共沸体系的最佳复合溶剂及配比。在最佳复合溶剂组成下,原共沸体系的相对挥发度达到最大值,该值优于组成复合溶剂的单溶剂所达到的分离效果。在最佳复合溶剂组成下,改变原料体系组成,复合溶剂组成对原料体系相对挥发度的影响趋势基本相同,这表明复合溶剂在萃取精馏塔内不同原料组成下均能较好地增加体系的相对挥发度,为工业上在萃取精馏过程中使用复合溶剂提供了理论依据。     

丙酮-四氢呋喃-水混合物的清洁分离工艺的概念设计

引言 四氢呋喃（THF）既是一种性能优良的贵重有机溶剂,又是一种重要的有机合成中间体,因此在制药、涂料、皮革等领域应用广泛．当四氢呋喃用作溶剂时,由于其不被消耗,往往需要进行回收．但四氢呋喃易与水、丙酮等其他极性溶剂形成共沸物,而生产中又常需要四氢呋喃的纯度足够高,进而增加了分离提纯难度．     

乙醇-水-离子液体三元体系的气液平衡测定及其萃取精馏试验

在101.32 kPa下,用改进的Othmer釜测定了乙醇-水-1,3-二甲基咪唑磷酸二甲酯盐([MMIM]+[DMP]-)物系等压气液平衡数据。实验结果表明,加入[MMIM]+[DMP]-使气液平衡线偏离乙醇-水二组分物系的气液平衡线,[MMIM]+[DMP]-含量越高,偏离程度越大;[MMIM]+[DMP]-表现出盐效应,使乙醇对水的挥发度发生改变,消除了乙醇-水物系的共沸点;并以[MMIM]+[DMP]-作为乙醇-水物系萃取精馏的溶剂,进行了萃取精馏的小型工艺试验,结果塔顶乙醇质量分数达到99.5%,能够满足工业要求。     

Heterogeneous extractive batch distillation of chloroform-methanol-water: Feasibility and experiments

A novel heterogeneous extractive distillation process is considered for separating the azeotropic mixture chloroform-methanol in a batch rectifying column, including for the first time an experimental validation of the process. Heterogeneous heavy entrainer water is selected inducing an unstable ternary heteroazeotrope and a saddle binary heteroazeotrope with chloroform (ternary diagram class 2.1-2b). Unlike the well-known heterogeneous azeotropic distillation process and thanks to continuous water feeding at the column top, the saddle binary heteroazeotrope chloroform-water is obtained at the column top, condensed and further split into the liquid-liquid decanter where the chloroform-rich phase is drawn as distillate. First, feasibility analysis is carried out by using a simplified differential model in the extractive section for determining the proper range of the entrainer flowrate and the reflux ratio. The operating conditions and reflux policy are validated by rigorous simulation with ProSim Batch Column^® where technical features of a bench scale distillation column have been described. Six reproducible experiments are run in the bench scale column matching the simulated operating conditions with two sequentially increasing reflux ratio values. Simulation and experiments agree well. With an average molar purity higher than 99%, more than 85% of recovery yield was obtained for chloroform and methanol.