Comparison of continuous homogenous azeotropic and pressure-swing distillation for a minimum azeotropic system ethyl acetate/nhexane separation

Continuous homogenous azeotropic distillation(CHAD) and pressure-swing distillation(PSD) are explored to separate a minimum-boiling azeotropic system of ethyl acetate and n-hexane. The CHAD process with acetone as the entrainer and the PSD process with the pressures of 0.1 MPa and 0.6 MPa in two columns are designed and simulated by Aspen Plus. The operating conditions of the two processes are optimized via a sequential modular approach to obtain the minimum total annual cost(TAC). The computational results show that the partially heat integrated pressure-swing distillation(HIPSD) has reduced in the energy cost and TAC by 40.79% and 35.94%, respectively, than the conventional PSD, and has more greatly reduced the energy cost and TAC by 62.61% and 49.26% respectively compared with the CHAD process. The comparison of CHAD process and partially HIPSD process illustrates that the partially HIPSD has more advantages in averting the product pollution, energy saving, and economy.

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.

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][Tf2N]),MeOH+DMC+1-ethyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide([Emim][Tf2N]),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][Tf2 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.

Process design and intensification of multicomponent azeotropes special distillation separation via molecular simulation and system optimization

This work provides an overview of distillation processes,including process design for different distillation processes,selection of entrainers for special distillation processes,system integration and intensification of distillation processes,optimization of process parameters for distillation processes and recent research progress in dynamic control strategies.Firstly,the feasibility of using thermodynamic topological theories such as residual curve,phase equilibrium line and distillation boundary line to analyze different separation regions is discussed,and the rationality of distillation process design is discussed by using its feasibility.Secondly,the application of molecular simulation methods such as molecular dynamics simulation and quantum chemical calculation in the screening of entrainer is discussed for the extractive distillation process.The thermal coupling mechanism of different distillation processes is used to explore the process of different process intensifications.Next,a mixed integer nonlinear optimization strategy for the distillation process based on different algorithms is introduced.Finally,the improvement of dynamic control strategies for different distillation processes in recent years is summarized.This work focuses on the application of process intensification and system optimization in the design of distillation process,and analyzes the challenges,prospects,and development trends of distillation technology in the separation of multicomponent azeotropes.

Prediction of Vapor-Liquid Equilibria of Alcohol-Hydrocarbon Systems by ^1H NMR and Azeotropic Point

With the energy parameters obtained from1H nuclear magnetic resonance(NMR)chemical shifts data by local composition model and coupled with azeotropic point,the low-pressure vapor-liquid equilibrium is satisfactorily predicted for alcohol+hexane,alcohol+cyclohexane,and alcohol+benzene binary systems at different temperatures.The relationship between the spectroscopic information and thermodynamic property is presented.

Investigation of energy-efficient heat pump assisted heterogeneous azeotropic distillation for separating of acetonitrile/ethyl acetate/n-hexane mixture

The conventional distillation is hard to accomplish the separation of acetonitrile/ethyl acetate/n-hexane mixture. Herein, a heterogeneous azeotropic distillation(HAD) without adding entrainer is proposed to separate ternary mixture. The proposed scheme is optimized via the simulated annealing algorithm and minimum total annual cost(TAC) is used as objective functions. To minimize energy consumption,heat pump is added on the basis of optimal heterogeneous azeotropic distillation and heat integration technology is used to further improve the energy recovery. The TAC, gas emission, energy consumption and exergy destruction are used to discuss the economy and environmental protection of processes.Among all the processes, the heat pump with higher preheating temperature(HPT) assisted HAD process by combining with heat integration(HAD-HPT-HI) has best performances on economic, environment,energy and exergy. Compared with conventional HAD process, the HAD-HPT-HI achieves the reductions of 52.17%, 68.86%, 65.87% and 65.46% on TAC, total energy consumption, gas emissions and exergy destruction, respectively.

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.

QSPR modeling of azeotropic temperatures and compositions for binary azeotropes containing lower alcohols using a genetic function approximation

Binary azeotropes, which contain two chemicals with a relative volatility of 1, are very common in the chemical industry. Understanding azeotropes is essential for effectively separating binary azeotropes containing lower alcohols. Experimental techniques and ab initio approaches can produce accurate results;however, these two processes are time consuming and labor intensive. Although thermodynamic equations such as UNIFAC are widely used, experimental values are required, and it is difficult to choose the best groups to represent a complex system. Because of their high efficiency and fast calculation speed, quantitative structure–property relationship(QSPR) tools were used in this work to predict the azeotropic temperatures and compositions of binary azeotropes containing lower alcohols. The QSPR models for 64 binary azeotropes based on centroid approximation and weighted-contribution-factor approximation were established using the genetic function approximation(GFA) procedure in Materials Studio software, and a leave-one-out cross-validation procedure was conducted.External tests of an additional 16 azeotropes were also investigated, and high determination coefficient values were obtained. The best QSPR models were explained in terms of the molecular structure of the azeotropes,and good predictive ability was obtained within acceptable prediction error levels.

Simulation and Analysis on Multiple Steady States of an Industrial Acetic Acid Dehydration System

In this work, an industrial acetic acid dehydration system via heterogeneous azeotropic distillation is simulated by Aspen Plus software. Residue curves are used to analyze the distillating behavior, and appropriate operating region of the system is determined. Based on steady states simulation, a sensitivity analysis is carried out to detect the output multiple steady states in the system. Different solution branches are observered when the flow rates of the feed stream and the organic reflux stream are selected as manipulated variables. The performance of the column under different steady states is different. A method is oroposed to achieve the desired steady state.

Separation process of butanol-butyl acetate-methyl isobutyl ketone system by the analysis to residual curve and the double effect pressure-swing distillation

The separation of ternary mixture of butanol, butyl acetate, and methyl isobutyl ketone(MIBK) was initially analyzed by the residual curve. In this process, MIBK was chosen as the azeotropic agent during the first step of separation. The optimum mass ratio of extra MIBK was 1.6 in the modified feed stream according to the residual curve. Thus on this condition the top product was butanol-MIBK azeotrope while the bottom product was butyl acetate in the preliminary separation of the mixture. Then the butanol and MIBK azeotrope was separated by the double effect pressureswing distillation with the low pressure column performing at 30 kPa and the atmospheric pressure column at 101 kPa. The optimal operating conditions were then obtained by using Aspen Plus to simulate and optimize the process. The results showed that the mass purities of butanol, butyl acetate, and MIBK were all more than 99% and reached the design requirements. Additionally, compared with the traditional distillation with outside heating, the double effect pressure swing distillation saved the reboiler duty by 48.6% and the condenser duty by 44.6%.

Effect of methylimidazolium-based ionic liquids on vapor–liquid equilibrium behavior of tert-butyl alcohol + water azeotropic mixture at 101.3 kPa

Three ionic liquids(ILs),1-ethyl-3-methylimidazolium bromine([EMIM]Br),1-butyl-3-methylimidazolium bromine([BMIM]Br),and 1-hexyl-3-methylimidazolium bromine([HMIM]Br),were used as the solvent for separation of {tert-butyl alcohol(TBA)+ water} azeotrope.Vapor–liquid equilibrium(VLE)data for {TBA + water + IL}ternary systems were measured at 101.3 k Pa.The results indicate that all the three ILs produce an obvious effect on the VLE behavior of {TBA + water} system and eliminate the azeotropy in the whole concentration range.[EMIM]Br is the best solvent for the separation of {TBA + water} system by extractive distillation among the three ILs.The experimental VLE data for the ternary systems are correlated with the NRTL model equation with good correlations.Explanations are given with activity coefficients of water and TBA,and the experimental VLE-temperature data for {TBA or water + IL} binary systems.

Process optimization of an industrial acetic acid dehydration progress via heterogeneous azeotropic distillation

The simulated process model of the HAc dehydration process under actual overloaded condition was conducted by amending the model of standard condition in our previous work using the process data collected from actual production. Based on the actual process model, the operation optimization analysis of each plant(HAc dehydration column, decanter and NPA recycle column) was conducted using Residue Curve Maps(RCMs),sensitivity analysis and software optimization module. Based on the optimized parameters, the influence of feed impurity MA and the temperature of decanter on the separating effect and energy consumption of the whole process were analyzed. Then the whole process operation optimizing strategy was proposed with the objective that the total reboiler duty Q Total of C-1 and C-3 reaches the minimum value, keeping C-1 and C-3 at their optimized separation parameters obtained above, connecting all the broken recycle and connection streams, and using the temperature of D-1 as operation variable. The optimization result shows that the total reboiler duty Q Total of the whole process can reach the minimum value of 128.32 × 10~6 k J·h^(-1) when the temperature of decanter is 352.35 K, and it can save 5.94 × 10~6 k J·h^(-1), about 2.56 t·h^(-1) low-pressure saturated vapor.

PREPARATION OF NANOMETER ZrO_2-8% Y_2O_3 POWDERS BY AZEOTROPIC DISTILLATION PROCESSING

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Research Progress on Azeotropic Distillation Technology

Azeotropic distillation is a special distillation method for separating liquid mixtures, which has better distillation effect and obvious advantages of energy saving and consumption reduction compared with traditional distillation. In this paper, the latest research progress of azeotropic distillation technology in separation, synthesis and energy saving at home and abroad is reviewed. The research progress in separation is reflected in product separation and product purification, and the research progress in energy saving is reflected in heat pump distillation and dividing wall column distillation respectively. Existing studies have shown that azeotropic distillation technology can produce higher purity target products than conventional distillation for the separation and purification of azeotropic or near-boiling compounds. Heat pump distillation and dividing wall column distillation are used in azeotropic distillation field, resulting in obvious energy-saving effect for distillation equipment. The follow-up research direction of new separation technology with the goal of reducing energy consumption and exploring new materials as entraining agents should be studied in detail, which provides certain guidance for the development of distillation technology in China’s chemical industry.

Preparation and Characterization of La_(0.8)Sr_(0.2)MnO_(3-δ) Cathode for SOFCs Fabricated Using Azeotropic Distillation Method

Strontium doped lanthanum manganite (LSM) powders were synthesized by three different routes: azeotropie distillation, sol-gel and solid state reaction respectively. The LSM samples, made by azeotropic distillation and sol-gel methods were prepared by firing at 1000℃for 6 h, and the LSM sample, made by solid state reaction method was produced by sintering at 1400℃for 18 h. The samples were characterized by XRD, TEC, SEM, EIS and polarization performance analysis. The results show that all the samples made by different methods have pure orthorhombic LSM phase, however exhibit different micro structure and electrochemical characterization, which relates to the different synthesis methods. The solid state reaction method produces the samples with larger particle size compared with azeotropic distillation and sol-gel methods. The powders made by azeotropic distillation method have less agglomerated particles compared with that made by sol-gel method because the precursor in the former is dispersed in n-butanol before sintering. The polarization current density of powder made by azeotropic distillation method was twice of that made by sol-gel method and four times of that made by solid state reaction method. The values of polarization resistance (Rp) are 0.35Ω·cm for the cathode synthesized by azeotropic distillation route, which is much lower than sol-gel (1.5Ω·cm2) and solid state reaction (2.3Ω·cm2) at 800℃.

SEPARATION OF FORMIC ACID-WATER AZEOTROPIC MIXTURES BY MEMBRANE DISTILLATION

The azeotrope disappeared when the formic acid-water mixtures were treated by membrane distillation. Membrane distillation were used for separation of formic acid-water azeotropic mixtures for the first time.

Isobaric vapor–liquid equilibrium for ternary system of ethanol, ethyl propionate and para-xylene at 101.3 kPa

Isobaric vapor–liquid equilibrium(VLE) data for the binary system ethyl propionate(2) + para-xylene(3) and ternary system ethanol(1) + ethyl propionate(2) + para-xylene(2) at atmospheric pressure(101.3 k Pa)were obtained by a VLE modified othmer still. All the experimental data passed a point to point consistency test of Van Ness method, which verified the data reliability. The Wilson and UNIQUAC activity coefficient models were employed to correlate the binary VLE data to obtain binary interaction parameters. Based on binary interaction parameters, ternary VLE data of ethanol(1) + ethyl propionate(2) + para-xylene(3) were predicted by Wilson and UNIQUAC models, which proved that predicted values are consistent with the experimental data.Furthermore, azeotropic phenomenon between ethanol and ethyl propionate disappears when the mole ratio of para-xylene and binary system of ethanol and ethyl propionate is 1:1. Therefore, this paper convinced that para-xylene is a proper extractive additive that could be used in extractive distillation to separate the binary azeotropic system of ethanol and ethyl propionate.

Azeotropic mixture used for development and validation of Lornoxicam in bulk and its tablet dosage form by spectrophotometric method

A novel,safe,economic and sensitive method of spectrophotometric estimation has been developed using Azeoptropic mixture (water∶methanol:60∶40,v/v) for the quantitative determination of Lornoxicam,a practically water-insoluble drug.Hence,Lornoxicam stock solution was prepared in Azeoptropic mixture.Lornoxicam showed maximum absorbance at 383 nm.Beer's law was obeyed in the concentration range 4-24 μg/mL with regression coefficient of 0.999.The method was validated in terms of linearity (R2=0.999),precision (CV for intra-day and inter-day was 0.28 0.68 and 0.12-0.92,respectively),accuracy (98.03-100.59％ w/w) and specificity.This method is simple,precise,accurate,sensitive and reproducible and can be used for the routine quality control testing of the marketed formulations.

Separation of isopropyl alcohol+isopropyl acetate azeotropic mixture:Selection of ionic liquids as entrainers and vapor-liquid equilibrium validation

Based on the COSMO-SAC model,1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium p-toluenesulfonate were selected from 30 ILs as entrainers to investigate the separation of the isopropyl alcohol+isopropyl acetate azeotrope.Two screening indicators,σ-profile and infinite dilution selectivity(S^(∞)),were adopted as the basis.The iso baric vapor-liquid equilibrium experiments for isopropyl alcohol+isopropyl acetate binary system and isopropyl alcohol+isopropyl acetate+confirmed ILs ternary systems were performed at the pressure of atmospheric pressure.The experimental measurement demonstrated that the adopt ILs enhanced the relative volatility of the above alcohol-ester azeotrope,leading to the elimination of the azeotropic point with a certain amount ILs.Meanwhile,the thermodynamic correlation for two systems containing ILs was explored with the NRTL model,which also reflects the extensive applicability of that by comparing the deviation between experimental and calculated data.And its binary interaction parameters were regressed,which can provide a basis for its simulation process.

Approach of Obtaining Liquor Flavoring From Yellow Water Based on Azeotropic Distillation

In order to extract the scarce natural liquor flavoring which is the dream of many liquor factories from yellow water,this research first added a proper amount of food-grade entrainer ethanol into yellow water,to form yellow water containing high content of ethanol.Then,the yellow water was subjected to azeotropic distillation and catalytic esterification,obtaining natural acetaldehyde,ethyl formate,ethyl acetate and esterification liquid containing various compounds that can influence the flavor of liquor.In the esterification liquid,the contents of ethyl propionate,ethyl butyrate,ethyl valerate,ethyl lactate and ethyl hexanoate are as higher as 19.0,46.5,1.5,39.8 and 137.1 g/L,respectively.The esterification liquid prepared by one fraction of yellow water can blend 9.14 fractions of common liquor into top-grade Luzhou-flavor liquor.Therefore,yellow water has great recycling value.