萃取精馏中离子液体萃取剂的研究进展

离子液体的低熔点和不挥发等特点使其较传统的萃取精馏萃取剂具有先天的优势,具有广泛的应用前景。本文介绍了离子液体作为萃取精馏萃取剂的研究进展,综述了汽液平衡法、无限稀释活度系数法等筛选离子液体萃取剂方法的研究成果以及目前用于计算含离子液体体系的相平衡模型研究进展,分析了离子液体萃取剂用于实用仍存在的问题,并展望了今后的研究方向。     

Influence of entrainer recycle for batch heteroazeotropic distillation

Dehydration of isopropanol applying batch heteroazeotropic distillation with toluene as entrainer (E) is investigated. The composition of the feed is near to that of the isopropanol (A)-water (B) azeotrope. The effects of recycling the entrainer and the off-cut are studied by dynamic simulation with a professional flow-sheet simulator. Three consecutive batches (one production cycle) is studied. Both operational modes (Mode I: decantation after distillation and Mode II: decantation during distillation) are simulated. For Mode II, calculations are performed both for Strategy A (distillate from the aqueous (E-lean) phase only) and Strategy B (partial withdrawal of the organic (Erich phase), as well). The E-rich phase, the final column hold-up and the off-cut (Mode II only) are recycled to the next batch. The influence of the following parameters are determined: quantity of entrainer, reflux ratios of the steps. The variations caused by the recycling in the 2^nd and 3^rd batches are also shown. The best results (lowest specific energy demand and highest recovery of A) are obtained by Mode II, Strategy A. Recycling increases the recovery, and drastically diminishes the entrainer consumption. However, it makes the production slower and decreases the quantity of fresh feed that can be processed.

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Use of glycerol as entrainer in the dehydration of bioethanol using extractive batch distillation: Simulation and experimental studies

In this paper the dehydration of bioethanol via extractive batch distillation using glycerol as entrainer is studied. Simulation and experimental tests were carried out in order to use glycerol to produce bioethanol with a composition higher than that of the azeotropic point. The results are compared to those reported using ethylene glycol and ionic liquids as entrainers for the same separation. The simulation and experimental results indicate that it is possible to produce high purity bioethanol that can be used as a fuel oxygenate. Among the entrainers used in the experimental tests, the glycerol presented the best performance in terms of the purity in the distillate. Also, it is important to highlight that glycerol has a lower cost in comparison to ethylene glycol and ionic liquids and that is considered a by-product in the biodiesel production.     

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.     

Modeling of batch extractive distillation

New data on the concentration profiles in a packed column during extractive distillation of benzene–heptane mixture in the presence of N-methylpyrrolidone as a separating agent have been obtained. A calculation method for the process based on partial mass transfer coefficients in the vapor and liquid has been proposed. The calculated and experimental data have been compared. It has been shown that both continuous and batch extractive distillation are calculated more precisely using the proposed model compared to the equilibrium model.     

Feasible separations and entrainer selection rules for heteroazeotropic batch distillation

A feasibility analysis is presented for the separation of close-boiling and azeotropic (minimum- and maximum-boiling) binary mixtures into pure components by the addition of an entrainer introducing a heterogeneous azeotrope. The analysis is done for both the conventional batch rectifier and the multivessel batch column. The analysis is theoretical and based on the assumptions of total reflux/reboil ratios and infinite number of stages. Two feasibility conditions are formulated that make it possible to investigate feasibility based on information coming solely from the distillation line map along with the binodal curve of the ternary mixture. Serafimov's classification is used for classifying the azeotropic phase diagrams. The feasibility analysis provides the necessary background and information for formulating rules for entrainer selection for the process. Two simple rules are then proposed, which make it possible to “screen” entrainers for heteroazeotropic batch distillation with minimum efforts.     

带塔底储罐的间歇萃取精馏的实验研究

提出了带塔底储罐的间歇萃取精馏操作方式.新操作方式使精馏过程中加入的溶剂及塔内回流液直接流入塔底储罐,不再返回塔釜.以乙二醇为溶剂分离乙醇–水共沸物的实验研究表明,新操作方式克服了普通间歇萃取精馏塔釜体积庞大的缺陷,同时具有塔釜温度稳定、加热容易控制、收率提高等优点.     

基于SIMULINK系统的间歇萃取精馏动态模拟

间歇萃取精馏属于非理想性极强的非稳态过程,很难找到一种快捷有效且易于执行的求解方法.基于此,分别建立了全回流开工、加溶剂全同流及产品采出3个阶段的平衡级动态模型,编写S函数将该模型求解过程嵌套于SIMULINK模块中,并在此基础上开发了间歇萃取精馏的动态模拟平台.通过将不同解法与实验值进行对比,确定了该研究条件下动态模型的求解策略:ODE45解法适于求解全回流开工和加溶剂全回流动态模型;ODE 15s解法和ODE 23s解法适于求解产品采出动态模型,其中ODE 23s的计算过程相对更快捷.     

间歇萃取精馏过程模拟计算

提出了一种可用于间歇萃取精馏过程模拟计算的快捷模型－准稳态模型，并对该方法的数学模型进行了推导。用此方法对间歇萃取精馏过程中塔顶、塔釜浓度，各塔板温度随时间的变化进行模拟，其结果与实验值吻合较好。它具有计算精度高、计算速度快等优点。     

分批萃取精馏回收无水乙醇的新工艺

针对分批萃取精馏法回收无水乙醇原有工艺流程中存在的问题,提出了优化方案。在原有流程的基础上,添加了一个溶剂回收釜,塔的下段液相流体直接流入溶剂回收釜。结果使得塔釜的温度变化降低,加热容易控制,操作时间变短。此方案对分批萃取精馏法回收无水乙醇的工艺改造有参考价值。     

带有中间储罐的间歇萃取精馏的模拟研究

本文提出了带有中间储罐塔间歇萃取精馏过程计算模型,将中间罐看成一块理论板,萃取剂看成第三组份进行建模,利用调节因子和泡点法相结合对整个塔进行迭代计算,经实例模拟表明,本模型只需较简单的赋初值,能以较快的速度收敛,本模型对带有中间储罐间歇萃取精馏操作及模拟具有一定的指导作用。     

间歇萃取精馏分离环戊烷–四氢呋喃–环己烷

根据环戊烷–四氢呋喃–环己烷的汽液平衡关系,通过选择适当的溶剂(N,N–二甲基甲酰胺),提出了采用同一溶剂分离三元混合物的间歇萃取精馏方法.考察了溶剂比对该三元物系间相对挥发度的影响,进行了实验室小试研究.实验结果表明,所选溶剂N,N–二甲基甲酰胺可以增大环戊烷-四氢呋喃的相对挥发度,同时也可使四氢呋喃–环己烷共沸物的共沸现象消失,实验室萃取精馏小试可以得到纯度高于99%的环戊烷和环己烷产品.     

间歇萃取精馏操作过程的实验研究

采用复合式精馏塔实现了萃取精馏的间歇操作,塔顶产品物质的量分数达95%以上。以取得合格产品的量与时间之比作为目标函数,研究了回流比R、中间回流量Vm(中间罐向提馏段进料流量)、萃取剂用量S对萃取精馏过程的影响,在R=5～10,Vm=3.2～7.2mL/min,S=1.2～2.2mL/min范围内,随以上操作参数的增大,目标函数均呈先增大后减小的趋势。     

N-甲基乙酰胺用于萃取精馏乙酸脱水过程机理

以N-甲基乙酰胺（NMA）作溶剂,用理论计算方法对萃取精馏醋酸脱水过程的作用机理进行研究。NMA与水\醋酸之间都有氢键形成,经计算得到NMA-醋酸复合物的稳定化能在-32.4~-44.3kJ/mol之间,且平面构型的NMA-醋酸复合物稳定能较高,而NMA与单分子水的稳定化能仅为-16.0kJ/mol。这说明NMA对醋酸具有选择性结合能力,使得醋酸不易挥发到汽相中去;这与VLE实验结果相一致,加入NMA可将水对醋酸的相对挥发度提高至3.0~4.0。用自然键轨道(NBO)分析表明,以上两种复合物形成过程中均伴随着电荷转移现象,整体上醋酸分子作为电荷受体而存在。     

混合溶剂间歇萃取精馏分离过程的模拟

由于混合溶剂存在"混合溶剂效应",能够解决简单溶剂选择性与互溶性相互矛盾的问题,因此混合溶剂间歇萃取精馏技术可以大大拓宽传统单一溶剂间歇萃取精馏分离技术的应用空间。文章建立了反映常规混合溶剂间歇萃取精馏过程的恒摩尔持液数学模型,并运用2点隐含法对其求解,结果表明,模拟计算结果与实验结果吻合较好。随后运用该模型探讨了塔身持液量、混合溶剂进料位置等因素对混合溶剂常规间歇萃取精馏的影响。得出以下结论,产品馏出速率随塔身持液量的增大而减小,塔顶馏分产量与塔身持液量的关系不大。另外,混合溶剂进料位置的选定对分离效果也有较大的影响,需要正确选择。     

双溶剂进口的双釜间歇萃取精馏

提出了带有塔底回收釜及双溶剂进口的间歇萃取精馏操作方式。在新操作方式中,塔内回流液不流回塔釜,而是流入塔底回收釜,再经简单蒸馏气相返回塔釜,回收后的溶剂返回精馏塔中。以乙二醇作溶剂分离乙醇-水物系的实验结果表明,当间歇操作次数为2时,产品采出率最大,单位产品消耗的新鲜溶剂量最少。新操作方式具有塔釜温度变化平稳,新鲜溶剂用量相对较少等优点。     

带有中间贮罐间歇萃取精馏实验研究

使用一个带有中间贮罐的间歇萃取精馏实验装置,以能形成最低共沸物的乙酸乙酯-乙醇体系为分离对象,选用N,N-二甲基甲酰胺(DMF)为萃取剂,实验研究了中间贮罐持液量、中间贮罐持液温度、萃取剂加入速率等操作参数对分离过程的影响。实验结果表明:随着萃取剂流率的增加,中间贮罐持液量也相应增加,组分更易于分离;随着中间贮罐持液量的增加,中间贮罐持液温度也相应升高,且存在最佳分离持液温度;萃取剂流率对分离结果的影响最大,中间贮罐持液温度对分离结果的影响次之,中间贮罐持液量对分离结果的影响最小。     

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.     

Choice of suitable entrainer in heteroazeotropic batch distillation system for acetic acid dehydration

Mixture containing acetic acid and water does not form azeotrope. However, because of tangent pinch on the pure water end, it is customary in industry to add an entrainer into this mixture to aid the separation via heterogeneous azeotropic distillation. When the production scale is relatively small, it is more beneficial to run the acetic acid dehydration in batch mode. In Chien et al. [Chien, I. L., K. L. Zeng, H. Y. Chao, and J. H. Liu, “Design and Control of Acetic Acid Dehydration System via Heterogeneous Azeotropic Distillation,” Chemical Engineering Science, 59, 4547 (2004)], a suitable entrainer for acetic acid dehydration operating in continuous mode was found to be iso-butyl acetate. This paper demonstrates that although iso-butyl acetate is a good entrainer for continuous heterogeneous azeotropic distillation system, it is not suitable in heteroazeotropic batch system for acetic acid dehydration. Instead, the performances of two other acetates are compared for the suggestion of better entrainer in batch operation. An extremely simple batch operating sequence for acetic acid dehydration will be demonstrated via dynamic simulation. The proposed batch operation is very robust in terms of the particular values chosen for the operating variables. This proposed batch operation gives very similar separation performance comparing to a multivessel operation and requires less process, instrumentation, and control equipments.     

以苯胺为溶剂间歇萃取精馏分离甲醇-乙腈

提出和研究了以苯胺作为溶剂的甲醇-乙腈间歇萃取精馏分离工艺。根据溶剂极性相似相溶原理,结合ChemCAD软件模拟汽液平衡和汽液平衡实验确定苯胺为合适的溶剂。结果表明,不仅苯胺能够消除甲醇-乙腈物系的共沸现象,效果优于N,N-二甲基甲酰胺（DMF）,而且可以采用Wilson模型对苯胺作为溶剂的甲醇-乙腈共沸物系汽液平衡进行模拟。通过实验考察了间歇萃取精馏的分离效果。采用有33块理论板的填料塔进行间歇萃取精馏甲醇-乙腈共沸混合物分离实验,其中净化回收段填料层3块理论板,萃取精馏段填料层30块理论板,回流比为4,苯胺作为溶剂,溶剂质量比为2.5∶1时,在塔顶得到产品甲醇质量分数为98.97%,高于DMF作为溶剂时的95.76%;表明苯胺更加适合作为萃取精馏分离甲醇-乙腈共沸物系的溶剂。