丁二烯萃取蒸馏新工艺

巴斯夫（BASF）的丁二烯萃取蒸馏工艺是以NMP（N-甲基吡咯烷酮）为溶剂的工艺，三种普遍用于丁二烯萃取溶剂中NMP是唯一无毒的溶剂。BASF公司投入了大量的精力改进了以NMP为溶剂的丁二烯萃取蒸馏的工艺。新工艺包括萃取蒸馏区。脱气区。蒸馏区和溶剂回收区。新工艺设备减少，投资降低10%，维护费用减少15%，装置安全性得到改善。     

A systematic synthesis framework for extractive distillation processes

An effective extractive distillation process depends on the choice of the extractive agent. In this contribution, heuristic rules for entrainer selection and the design of entrainers through computer-aided molecular design are reviewed. The potential of the generated alternatives is then evaluated by their selectivity at infinite dilution and by the rectification body method (RBM). It is shown that a screening based on selectivity alone is not sufficient and could possibly lead to an unfavorable entrainer choice. The minimum entrainer flowrate and the minimum energy demand, calculated from the RBM, allow a more comprehensive evaluation of different entrainer alternatives. In a third step a rigorous mixed-integer optimization of the entire extractive flowsheet for the remaining entrainer candidates is executed to fix the remaining design degrees of freedom and to determine the best entrainer. Since a number of alternative entrainers have already been eliminated, only a few optimizations are necessary. These steps form a framework which facilitates the systematic generation and evaluation of entrainer alternatives. The suggested synthesis framework is illustrated with a case study where acetone and methanol are to be separated.     

Economic evaluation of energy saving alternatives in extractive distillation process

Until now, there has not been consensus about the superiority of thermally coupled sequence over the conventional sequence in the extractive distillation process. In this sense, the main goal of this paper is to analyze three approaches for saving energy in the extractive distillation process: optimization, thermal integration and thermal coupling. Three azeotropic mixtures were investigated: ethanol and water (M1); tetrahydrofuran and water (M2); and acetone and methanol (M3). The solvents were ethylene glycol for M1 and M2, and water for M3. The results are shown in terms of the total annual cost (TAC) and specific energy consumption (SEC), and revealed that a thermally coupled extractive distillation sequence with a side rectifier did not always present the best results. Taking the case studies from literature as a starting point (without thermal integration), the optimization procedure used in this work found that TACs are always lower. The inclusion of thermal integration in configurations led to reducing TAC for all mixtures under investigation when compared to the sequences without this integration. When comparing two modifications in the layout of extractive distillation, it can be seen that it is more advantageous to use the preheating of the azeotropic feed with the recycle stream from the recovery column of the conventional sequence than using a thermally coupled sequence.     

Simulated annealing-based optimal design of energy efficient ternary extractive dividing wall distillation process for separating benzene-isopropanol-water mixtures

This article investigates the performances of different extractive distillation processes intensified with dividing-wall column for separating benzene-isopropanol-water ternary mixtures. All the processes with ethylene glycol as solvent are optimized with the minimal total annual cost (TAC) as target. In order to get the global optimal solution intelligently, an improved simulated annealing algorithm is adopted, which is programmed in MATLAB and linked to Aspen Plus. The results show that the extractive dividing wall column-solvent (EDWC-S) process consisting of an extractive dividing wall column and a solvent recovery column is the best scheme. It can reduce the TAC by 28.65％and CO2 emissions by 32.84％com-pared to the conventional triple-column extractive distillation process.     

Conceptual process design of extractive distillation processes for ethylbenzene/styrene separation

In the current styrene production process the distillation of the close-boiling ethylbenzene/styrene mixture to obtain an ethylbenzene impurity level of 100 ppm in styrene accounts for 75–80% of the energy requirements. The future target is to reach a level of 1–10 ppm, which will increase the energy requirements for the distillation even further. Extractive distillation is a well-known technology to separate close-boiling mixtures up to high purities. The objective of this study was to investigate whether extractive distillation using ionic liquids (ILs) is a promising alternative to obtain high purity styrene. Three ILs were studied: [3-mebupy][B(CN)₄], [4-mebupy][BF₄], and [EMIM][SCN]. Extractive distillation with sulfolane and the current conventional distillation process were used as benchmark processes. The IL [4-mebupy][BF₄] is expected to outperform the other two ILs with up to 11.5% lower energy requirements. The operational expenditures of the [4-mebupy][BF₄] process are found to be 43.2% lower than the current distillation process and 5% lower than extractive distillation with sulfolane extractive distillations. However, the capital expenditures for the sulfolane process will be about 23% lower than those for the [4-mebupy][BF₄] process. Finally, the conclusion can be drawn from the total annual costs that all studied extractive distillation processes outperform the current distillation process to obtain high purity styrene, but that the ILs evaluated will not perform better than sulfolane.     

环己烯-己烷萃取精馏塔系统的改进

采用新型填料塔技术和新的工艺流程,对原环己烯分离塔系统进行改造,改造后环己烯分离塔塔顶环己烯从6.5%下降到4.0%,环己烯回收塔塔顶环己烷从3.5%～4%下降到2.5%,环己烯纯度从95%提高到97%以上。     

Effect of thermodynamic parameters on prediction of phase behavior and process design of extractive distillation

Extractive distillation was investigated for separation of the minimum azeotrope of n-propanol/water,via the Aspen Plus simulation platform.Experimental data of n-propanol/water,which could pass the thermodynamic consistency test,were regressed to get suitable binary interaction parameters (BIPs) by the UNIQUAC thermodynamic model.The azeotrope system was heterogeneous in the simulation with built-in BIPs,which was contrary to the experimental data.The study focused on the effect of thermodynamic parameters on the prediction of phase behavior,and process design of extractive distillation.N-methyl-2-pyrrolidone (NMP) and ethylene glycol were used as solvents to implement the separation.Processes with built-in and regressed BIPs were explored,based on the minimum total annual cost (TAC).There were significant differences in the phase behavior simulation using different thermodynamic parameters,which showed the importance of BIPs in the design and optimization of extractive distillation.     

Conceptual design of an extractive distillation process for the separation of azeotropic mixture of n-butanol-isobutanol-water

In many chemical processes, large amounts of wastewater containing butanol and isobutanol are produced. Given that n-butanol-isobutanol-water can form triple azeotrope, high-purity butanol cannot be recovered from the wastewater by ordinary distillation. To economically and effectively recover butanol from this kind of wastewater, 1,4-butanediol is selected as an extractant to break the formation of the azeotropes, and a doubleeffect extractive distillation process is proposed. The conceptual design of the proposed process is accomplished based on process simulation. With the proposed process, the purity of recovered butanol and water is greater than 99.99 wt%. In comparison with the conventional azeotropic distillation process, economic analysis shows that the operating cost of the proposed process is lower:when the capacity of wastewater treatment is 100 t·h^-1, the total operating cost decreases by 5.385×10⁶ USD per year, and the total annual cost of the new process decreases by 5.249×10⁶ USD per year. In addition, in the extractive distillation system, variable effects on separation purities and cost are more complex than those in the ordinary distillation system. The method and steps to optimize the key variables of the extractive distillation system are also discussed in this paper and can provide reference for similar studies.     

Batch extractive distillation as a hybrid process: separation of minimum boiling azeotropes

The batch extractive distillation is compared with the hybrid process (absorption+distillation) by feasibility studies and rigorous simulation. A new method is presented for the assessment of feasibility of the hybrid batch extractive distillation. The limiting values of the operational parameters are determined. Calculations are presented for the separation of the minimum boiling azeotropic mixtures of acetone-methanol and ethanol-water by the application of water and ethylene glycol as heavy solvents, respectively.     

Optimal retrofit design of extractive distillation to energy efficient thermally coupled distillation scheme

Design and optimization procedures employing the response surface methodology (RSM) for retrofitting the conventional extractive distillation sequence to a thermally coupled extractive distillation scheme (TCEDS—SR) is presented. The optimum TCEDS—SR structure can be found in a practical manner with minimal simulation runs. Furthermore, the RSM allows the interactions between variables to be identified and quantified. The separation of close boiling point mixtures and azeotropic mixtures was examined to test the proposed method. The predictions agreed well with the results of a rigorous simulation. The results showed that a retrofit of the extractive distillation sequence to TCED—SR can achieve significant energy savings compared to the conventional extractive distillation sequence. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1175–1182, 2013     

缩短萃取蒸馏单元的开工时间

简述了粗苯加氢精制过程中萃取蒸馏单元的工艺流程,阐述了萃取蒸馏单元停工后开工的操作以及开工过程中出现的问题,分析了影响开工时间的因素,提出了缩短开工时间的方案和工艺,改进后可节约能耗,增加利润。     

Systematic screening procedure and innovative energy-saving design for ionic liquid-based extractive distillation process

In the traditional extractive distillation process, organic solvents are often used as entrainers. However, environmental influence and high energy-consumption are significant problems in industrial application. In this study, a systematic screening strategy and innovative energy-saving design for ionic liquid-based extractive distillation process was proposed. The innovative energy-saving design focused on the binary minimum azeotrope mixtures isopropanol and water. Miscibility, environmental impact and physical properties (e.g., melting point and viscosity) of 30 ionic liquids were investigated. 1-Ethyl-3-methyl-imidazolium dicyanamide and 1-butyl-3-methyl-imidazolium dicyanamide were selected as candidate entrainers. Feasibility analysis of these two ionic liquids was further performed via residue curve maps, isovolatility line and temperature profiles. An innovative ionic liquid-based extractive distillation process combining distillation column and stripping column was designed and optimized with the objective function of minimizing the total annualized cost. The results demonstrate that the total annualized cost was reduced by 19.9% with 1-ethyl-3-methyl-imidazolium dicyanamide as the entrainer and by 24.3% with 1-butyl-3-methyl-imidazolium dicyanamide, compared with that of dimethyl sulfoxide. The method proposed in this study is conducive to the green and sustainable development of extractive distillation process.     

生物燃料乙醇分壁塔萃取精馏新工艺的研究

针对生物燃料乙醇生产中的"蒸馏-脱水"过程,建立基于分壁式萃取精馏塔的三塔工艺和两塔工艺,对2种工艺进行模拟计算,比较其分离效果和过程能耗。结果显示,在满足产品质量的前提下,三塔工艺比两塔工艺节约66.6%的冷凝器热负荷和77.9%的再沸器热负荷。对三塔工艺的分壁式萃取精馏塔的工艺条件进行优化,优化结果为,主塔回流比1.5,溶剂比1.0,原料进料位置为第22块板,隔板底端位置在第28块板,气相分配比为8.4。在优化工艺条件下对三塔工艺进行全流程模拟,可得到质量分数99.96%生物燃料乙醇和99.49%的水,回收萃取剂乙二醇质量分数为99.97%。     

Design and control of acetonitrile/N-propanol separation system via extractive distillation using N-methyl pyrrolidone as entrainer

The extractive distillation process for separating a binary azeotrope of acetonitrile and n-propanol is investigated using N-methyl pyrrolidone as entrainer. On the basis of multiparameter optimization, a design with optimized operation conditions for the process is presented. Two dynamic control structures are proposed. Feed disturbances are used to evaluate the dynamic performance. The response results reveal that the control structure CS1 with temperature–composition cascade control loop can handle all the disturbances and maintain product purities, except one large transient deviation, while the improved control structure CS2 with average temperature control loop can overcome this obstacle and handle disturbances effectively.     

旋转填料床间歇萃取精馏性能研究

为了寻找强化间歇萃取精馏过程的有效途径,在装填2mm×2mm三角形螺旋填料的旋转床中,以乙醇-水为实验物系,乙二醇为萃取剂,通过考察馏出液组成随时间的变化情况,产品的纯度和回收率随转速、回流比和溶剂比的变化情况,研究了旋转填料床间歇萃取精馏的性能。结果表明,旋转填料床中强大的离心力和高效填料的协同作用极大地强化了间歇萃取精馏过程,具有分离效果好、操作时间短、节能、小设备大生产能力等突出优点;存在最佳转速使产品的纯度和回收率最大;增加溶剂比和回流比均能使产品的纯度和回收率得到提高,但增加溶剂比的效果更显著。旋转填料床是强化间歇萃取精馏过程的有效途径。     

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。     

Reducing the energy demand of corn‐based fuel ethanol through salt extractive distillation enabled by electrodialysis

The thermal energy demand for producing fuel ethanol from the fermentation broth of a contemporary corn‐to‐fuel ethanol plant in the U.S. is largely satisfied by combustion of fossil fuels, which impacts the possible economical and environmental advantages of bioethanol over fossil fuels. To reduce the thermal energy demand for producing fuel ethanol, a process integrating salt extractive distillation—enabled by a new scheme of electrodialysis and spray drying for salt recovery—in the water‐ethanol separation train of a contemporary corn‐to‐fuel ethanol plant is investigated. Process simulation using Aspen Plus® 2006.5, with the electrolyte nonrandom two liquid Redlich‐Kwong property method to model the vapor liquid equilibrium of the water‐ethanol‐salt system, was carried out. The integrated salt extractive distillation process may provide a thermal energy savings of about 30%, when compared with the contemporary process for separating fuel ethanol from the beer column distillate. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

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。     

DMF萃取精馏法分离丁二烯的工艺流程模拟

利用ASPEN PLUS化工流程模拟软件,对DMF法丁二烯装置中的第一萃取精馏塔进行了模拟,与实际生产装置的工艺参数对比表明:模拟计算的结果是准确的。根据模拟计算的结果,分析了溶剂烃比、回流比、溶剂进塔温度等工艺参数对分离过程的影响,并提出了优化的工艺条件。     

Optimal biocompatible solvent design for a two-stage extractive fermentation process with cell recycling

In this study, crisp and fuzzy multiple-goal optimization approaches are respectively introduced to design an optimal biocompatible solvent to a two-stage extractive fermentation with cell recycling for ethanol production. When designing a biocompatible solvent for the extractive fermentation process, many issues, such as extractive efficiency, conversion, amount of solvent utilized and so on, have to be considered. An interactive multiple-goal design procedure is introduced to determine a trade-off result in order to satisfy such contradicted goals. Both approaches could be iterated to solve the interactive multiple-goal design problem in order to yield a trade-off result. However, the crisp optimization design is a tedious task that requires the designer to provide various pairs of the upper bounds for the design problem to obtain the corresponding solution. The fuzzy optimization approach is able to be trade-off several goals simultaneously and to yield the overall satisfactory grade for the product/process design problem.