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 on nondominated sorting genetic algorithm II optimizes the pressure and the amount of solvent cooperatively to avoid falling into the optimal local solution.Based on the optimal process parameters,the proposed heat-integrated process can reduce the gas emissions by 29.30%.The heat-integrated ED,further coupled with the pervaporation process,can reduce gas emission by 42.36%and has the highest exergy efficiency of 47.56%.In addition,based on the heat-integrated process,the proposed two heat pump assisted heat-integrated ED processes show good economic and environmental performance.The double heat pump assisted heat-integrated ED can reduce the total annual cost by 28.78%and the gas emissions by 55.83%compared with the basis process,which has a good application prospect.This work provides a feasible approach for the separation of ternary azeotropes.

Economy, environmental assessment and energy conservation for separation of isopropanol/diisopropyl ether/water multi-azeotropes via extractive distillation coupled pervaporation process

This wok proposed the extraction distillation coupled pervaporation(ED+PV) technology process using two different solvents to separate isopropanol(IPA) and diisopropyl ether(DIPE) from DIPE/IPA/H_(2)O ternary heterogeneous azeotropes in industrial wastewater from the synthesis of isopropanol in this study.Based on strict design specifications, simulation and sequential iteration methods are used for process design and optimization. Compared to the ethylene glycol(EG)-EG+H_(2)O process and the 1,3-propanediol(PDO)-IPA+H_(2)O process, the total annual cost(TAC) of the EG-IPA+H_(2)O process decreased by 20.76% and 7.86%(PDO). Compared to the EG-EG+H_(2)O process, the TAC of the PDO-IPA+H_(2)O process reduced 14%, but the global warming potential(GWP) and human toxicity of the PDO-IPA+H_(2)O process increased 11.3% and 4.07% respectively. Compared to the PDO-IPA+H_(2)O process, the EG-IPA+H_(2)O process saves 7.86%(TAC), 9.78%(GWP) and 9.85%(human toxicity). The ED+PV process with EG is superior to PDO in factors of TAC, energy consumption, human toxicity and environment. The EG-IPA+H_(2)O process changed the separation order of the products of the multi-azeotropic system, reduced the cost and energy conservation of the system, and enhanced the environmental protection evaluation of the process, is the best process through life cycle assessment for analyzing the economy, energy conservation, environmental assessment and human toxicity, designing cleaner products, controlling waste discharge, and promoting the chemical purification industry. This work provides a new process design and optimized separation ideas, will have a good guiding significance for the research and application separation of multi-azeotropic mixture with mixed solvents in organic wastewater from the cleaner chemical production, has been up to standard wastewater discharge process, and realized the development goal of carbon peak and carbon neutrality in the sustainable development of chemical clean industry.

Economic and entropy production evaluation of extractive distillation and solvent-assisted pressure-swing distillation by multi-objective optimization

Extractive distillation(ED)and solvent-assisted pressure-swing distillation(SA-PSD)are both special distillation processes that perform good at separating pressure-insensitive azeotropes.However,few reported studies have compared the performance of the two processes.In this paper,ED processes with N-methylpyrrolidone(NMP)and dimethlac-etamide(DMCA)as entrainer,SA-PSD process with isopropyl-alcohol(IPA)as solvent and SA-PSD process with partial heat integration(PHI-PSD)are proposed to achieve high purity separation of a mixture of cyclohexane/2-butanol system.The optimal operating conditions of the processes are obtained after optimizing with NSGA-Ⅱ algorithm when total annual cost(TAC)and the entropy production of process are set as objectives.The optimal results show that the optimal PHI-PSD process has lower TAC by 28.7% and the lower entropy production by 39.5% than the optimal SA-PSD process while the ED process with NMP as entrainer has lower TAC by 50.9% and the lower entropy production by 56.1% than the optimal SA-PSD process.The optimal results show that the ED process with NMP as entrainer has the best economic and thermodynamic efficiency among the four proposed processes in this paper.

Extractive distillation: Advances in conceptual design, solvent selection,and separation strategies

Extractive distillation(ED) is one of the most promising approaches for the separation of the azeotropic or closeboiling mixtures in the chemical industry. The purpose of this paper is to provide a broad overview of the recent development of key aspects in the ED process involving conceptual design, solvent selection, and separation strategies. To obtain the minimum entrainer feed flow rate and reflux ratio for the ED process, the conceptual design of azeotropic mixture separation based on a topological analysis via thermodynamic feasibility insights involving residue curve maps, univolatility lines, and unidistribution curves is presented. The method is applicable to arbitrary multicomponent mixtures and allows direct screening of design alternatives. The determination of a suitable solvent is one of the key steps to ensure an effective and economical ED process. Candidate entrainers can be obtained from heuristics or literature studies while computer aided molecular design(CAMD) has superiority in efficiency and reliability. To achieve optimized extractive distillation systems, a brief review of evaluation method for both entrainer design and selection through CAMD is presented. Extractive distillation can be operated either in continuous extractive distillation(CED) or batch extractive distillation(BED), and both modes have been well-studied depending on the advantages in flexibility and low capital costs. To improve the energy efficiency, several configurations and technological alternatives can be used for both CED and BED depending on strategies and main azeotropic feeds. The challenge and chance of the further ED development involving screening the best potential solvents and exploring the energy-intensive separation strategies are discussed aiming at promoting the industrial application of this environmentally friendly separation technique.

Computer-aided ionic liquid design for alkane/cycloalkane extractive distillation process

A computer-aided ionic liquid design(CAILD) study is presented for the frequently encountered alkane/cycloalkane separations in petrochemical industry. Exhaustive experimental data are first collected to extend the UNIFAC-IL model for this system, where the proximity effect in alkanes and cycloalkanes is considered specifically by defining distinct groups. The thermodynamic performances of a large number of ILs for 4 different alkane/cycloalkane systems are then compared to select a representative example of such separations. By applying n-heptane/methylcyclohexane extractive distillation as a case study, the CAILD task is cast as a mixed-integer nonlinear programming(MINLP) problem based on the obtained task-specific UNIFAC-IL model and two semi-empirical models for IL physical properties. The top 5 IL candidates determined by solving the MINLP problem are subsequently introduced into Aspen Plus for process simulation and economic analysis, which finally identify 1-hexadecyl-methylpiperidinium tricyanomethane([C_(16)MPip][C(CN)_3]) as the best entrainer for this separation.

Extractive Distillation of Methyl Acetate-Methanol Azeotrope Using [DMIM]DMP as Solvent

In order to separate methyl acetate and methanol azeotrope, the ionic liquid(IL) 1,3-dimethylimidazolium dimethylphosphate([DMIM]DMP) was used as the solvent. The Aspen Plus software was used to design and optimize the extractive distillation process. Under the optimized conditions, the mass fractions of methyl acetate and methanol were both above 99.5%. Compared with the dimethyl sulfoxide(DMSO) process, the [DMIM]DMP process has the advantages of saving energy and lower equipment investment cost. The result shows that using [DMIM]DMP as the solvent to separate a methyl acetate and methanol azeotrope has better prospect in industrial application.

Design, Optimization and Control of Extractive Distillation for Separation of Ethyl Acetate-Ethanol-Water Mixture Using Ionic Liquids

In this work, the process simulation of pressure-swing distillation(PSD) and extractive distillation(ED) using ionic liquid(IL) 1-butyl-3-methylimidazolium acetate([bmim][OAc]) as the entrainer for separation of ethyl acetateethanol-water mixture is performed. The design parameters of the two distillation processes are optimized with the minimum total annual cost(TAC) serving as the objective function. The results show that the TAC saving of ED process is 35.27% in comparison with that of PSD process in the case of achieving the same purity and yield of ethyl acetate.In addition, the dynamic controllability of ED process is further studied. The traditional two-point temperature control structure is proposed for the ED process, and it works pretty well while taking into account the disturbances in both feed rate and feed composition.

Extractive distillation of the benzene and acetonitrile mixture using an ionic liquid as the entrainer

The benzene and acetonitrile azeotropic mixture was proposed to be separated by extractive distillation using an ionic liquid(IL)as the entrainer.The suitable IL was selected by the COSMO-RS model,and 1-ethyl-3-methylimidazolium tetrafluoroborate([EMIM][BF_(4)])was considered as the suitable entrainer mainly due to its high selectivity,low viscosity,and low price.The experimental vapor pressure data of the IL-containing systems(benzene+[EMIM][BF_(4)]and acetonitrile+[EMIM][BF_(4)])were measured in the full concentration range.The results show that acetonitrile has a stronger interaction with IL than benzene,and the low deviations between the experimental and UNIFAC predicted values show the reliability of the UNFIAC model.The UNIFAC predicted vapor-liquid equilibrium data of the benzene+acetonitrile+dimethyl sulfoxide(DMSO)/[EMIM][BF_(4)]system show that the relative volatility of benzene to acetonitrile is higher when the entrainer is[EMIM][BF_(4)].The process simulation results show that[EMIM][BF_(4)]can reduce the material and energy consumptions compared with DMSO.

Molecular interaction mechanism in the separation of a binary azeotropic system by extractive distillation with ionic liquid

Ionic liquids(ILs)have shown excellent performance in the separation of binary azeotropes through extractive distillation[1].But the role of the ionic liquid in azeotropic system is not well understood.In this paper,COSMO-RS model was applied to screen an appropriate IL to separate the binary azeotrope of ethyl acetate(EA)and ethanol and 1-octyl-3-methylimidazolium tetrafluoroborate([OMIM][BF4])was selected.The Quantum Mechanics(QM)calculations and molecular dynamics(MD)simulation are performed to study the interactions between the solvent molecules and[OMIM][BF4],in order to investigate the separation mechanism at the molecular level.The nature of the interactions is studied through the reduced density gradient(RDG)function and quantum theory of Atom in Molecule(QTAIM).Hydrogen bonds and van der Waals interactions are the key interactions in the complexes.The results of MD simulations indicate that the introduction of ILs has a prominent effect on the interaction between the solvent molecules,especially on reducing the number of hydrogen bonds among the solvent molecules.The radial distribution function(RDF)reveals that the interaction between the cation and solvent molecules will increase while the concentration of ILs increases.This paper provides important information for understanding the role of ILs in the separation of the azeotropic system,which is valuable to the development of new entrainers.

[EMIM][DCA] as an entrainer for the extractive distillation of methanol-ethanol-water system

The ionic liquid(IL)1-ethyl-3-methylimidazolium dicyanamide([EMIM][DCA])was selected as an appropriate entrainer for the extractive distillation of the methanol-ethanol-water mixture.The COSMO-RS model was applied to screen out the appropriate solvents considering selectivity and solvent capacity together.Isobaric vapor-liquid equilibrium(VLE)experiments for the two systems of methanol-water and ethanol-water with different amounts of[EMIM][DCA]added were conducted at 101.3 kPa.The experimental data showed that[EMIM][DCA]exhibits an obvious salting effect for the methanol(or ethanol)-water mixture and eliminates the azeotropic point of ethanol-water.Moreover,the predicted values by UNIFAC-Lei model coincide well with experimental data.The separation mechanism was further explained in combination with surface charge density distribution(σ-profiles),excess enthalpy(HE),and binding energy.In addition,the flow charts were designed to evaluate the improvement of energy consumption with[EMIM][DCA]as the entrainer when compared to ethylene glycol(EG).The simulation results demonstrated that[EMIM][DCA]is more energy efficient than EG.

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 simulatedby a constant holdup model and solved by two point implicit method. Acetone and methanol mixture was separatedin such a setup using water as solvent. The simulation agrees well with experimental results. The experimental andsimulation results show that the solvent at the bottom and the product at the top of the column can be withdrawnsimultaneously for a long period of time. It needs more time for the solvent to reach high purity than that requiredfor the more volatile component to reach high purity, so that the time to withdraw solvent from the bottom isdelayed.

Simulation of 1,3-Butadiene Production Process by Dimethylfomamide Extractive Distillation

现在，引得出的蒸馏是主要技术生产 1,3 丁二烯。这研究由白杨随 DMF 引得出的蒸馏模仿了 1,3 丁二烯生产过程加。溶剂比率是引得出的蒸馏过程的最重要的参数。文章给出合适的溶剂比率，倒流比率，精华比率，和列的底部产品比率。它也讨论热大量几列。模拟的结果因而与植物数据，它与对方一起显示出好一致相比。

Simulation for Transesterification of Methyl Acetate and n-Butanol in a Reactive and Extractive Distillation Column Using Ionic Liquids as Entrainer and Catalyst

有 entrainer 和催化剂(RED-IL ) 被建议与 n-butanol 由甲基醋酸盐的 transesterification 反应生产甲醇和 n 丁基醋酸盐的离子的液体的一个新反应、引得出的蒸馏过程。RED-IL 过程经由一个严密模型，和甲醇的高纯净产品被模仿， n 丁基醋酸盐能在如此的一个过程被获得。倒流比率的效果，喂模式，劫盗，喂地点， entrainer 比率和催化剂 RED-IL 过程上的集中被调查。甲基醋酸盐的变换和有在列， entrainer 比率和催化剂内容的劫盗的产品增加的纯净。最佳的倒流比率在 RED-IL 过程存在。比作混合喂模式，分离喂模式是更有效的，在哪个最佳喂反应物的地点存在。

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 CO_(2) emissions by 32.84% compared to the conventional triple-column extractive distillation process.

A Quasi-steady-state Model for Numerical Simulation of Batch Extractive Distillation

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 experimental 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.

Design and Operation of Batch Extractive Distillation with Two Reboilers

This paper proposes a modified operation mode of batch extractive distillation with two reboilers.The separation of ethanol and water using as ethylene glycol is well done to validate the feasibility of this mode.The pilot-plant experimental data under the identical operational conditions between the regular mode and the modified mode are in particular discussed.The studied results prove more practical advantages of the modified mode over the regular mode such as easier operation control,more flexibility and higher separation efficiency etc.So it supplies certain guidance for the industrial application of batch extractive distillation process.

The Separation of Catechol from Carbofuran Phenol by Extractive Distillation

在这研究，引得出的蒸馏被使用了用高纯净和产量从 carbofuran 酚(CFP ) 分开儿茶酚(猫) 。到猫的 CFP 的相对轻快被测量，并且分开代理人的选择被调查。试验性的结果显示 CFP/CAT 是有在 93.40 &#xb0 的一个 azeotropic 点的一个 azeotropic 系统； C/0.400 kPa 和包含 49.96% CFP 和 50.04% 猫的 azeotropic 混合物。从相对轻快的决心的数据显示出那分开象 diglycol 那样的代理人， 4-butylcatechol (4-TBC ) 能增加相对轻快直到 1.90。在一射击过程批有 3% 的 CFP 混合的引得出的蒸馏(由质量) 分别地，当没有分开代理人的蒸馏提供了纯净和收益时， diglycol 作为分开获得的 CFP 的代理人，纯净和产量是 99.0% 和 95.0% 仅仅 98.0% 和 90.0% 分别地。没有剩余，分开在产品发现的代理人。

Behaviour of Tributylamine as Entrainer for the Separation of Water and Acetic Acid with Reactive Extractive Distillation

A new separation method, reactive extractive distillation, was put forward for separating water and acetic acid. The separation mechanism was analyzed through infrared spectra technique. Isobaric vapor-liquid equilibrium (VLE) data at 101.33 kPa for the binary or ternary systems consisting of water, acetic acid and tributylamine were measured. The activity coefficients were correlated by using Wilson, NRTL, and UNIQUAC Equations.The VLE experiment showed that tributylamine could enhance the relative volatility of water to acetic acid. An extractive distillation experiment was carried out and proved that tributylamine was a good extractive solvent.

Solvent Selection for Extractive Distillation by the Universal Quasichemical Functional Group Activity Coefficient(UNIFAC) Group Contribution Method

A method to select solvent for extractive distillation is proposed by UNIFAC group contribution. Solventselectivity can be divided into two parts: the partial combinatorial solvent selectivity and the partial residual solventselectivity. The properties of partial combinatorial and residual solvent selectivity are demonstrated. In most cases,the partial residual solvent selectivity is predominant. The candidate groups of solvent can be selected by groupinteraction parameter using UNIFAC group interaction parameter table as a guide.

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 ×10~6 USD per year, and the total annual cost of the new process decreases by 5.249 ×10~6 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.