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.

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.

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.

Dynamic control analysis of interconnected pressure-swing distillation process with and without heat integration for separating azeotrope

Dynamic controls of pressure-swing distillation with an intermediate connection(PSDIC) process of ethyl acetate and ethanol separation were investigated.The double temperature/composition cascade control structure can perfectly implement effective control when ±20% feed disturbances were introduced.This control structure did not require the control of the flowrate of the side stream.The dynamic controllability of PSDIC with partial heat integration(PHIPSDIC) was also explored.The improved control structure can effectively control ±20% feed disturbances.However,in industrial production,simple controller,sensitive and easy to operate,is the optimal target.To avoid the use of component controllers or complex control structure,the original product purities could be maintained using the basic control structure for the PSDIC process if the product purities in steady state were properly increased,albeit by incurring a slight rise in the total annual cost(TAC).This alternative method without a composition controller combined with the energy-saving PSDIC process provides a simple and effective control scheme in industrial production.

Separation of fuel additives based on mechanism analysis and thermodynamic phase behavior

tert-butanol and ethyl acetate,as fuel additives and oxygenated fuels,can improve fuels quality and reduce exhaust emissions.Therefore,the recovery of these compounds from azeotropic systems is of great significance.Ionic liquids(ILs)are promising green solvents for separating azeotropic systems.In this study,an efficient extraction strategy based on 1-butyl-3-methylimidazolium acetate([Bmim][AC])is proposed.The mechanism by which ILs enable the separation of binary alcohol-ester azeotropes was revealed by evaluating the lowest conformational energy through combining an independent gradient model based on the Hirshfeld partition(IGMH)and frontier molecular orbitals,to preliminarily screen the extractants.The range of extractants was further reduced by a vapor–liquid phase equilibrium(VLE)experiment,and a modeling method for separating the alcohol–ester system and recovering the solvent using[Bmim][AC]and 1-ethyl-3-methyl-3-imidazolium acetate([Emim][AC])is established.Under the optimal operating conditions,the use of[Bmim][AC]can reduce the total annual cost(TAC)per year by 17.78%,and the emissions of CO_(2),SO_(2),and NO can be reduced by 10.86%.In this study,a comprehensive method for screening extractants is proposed,and the simulation process is optimized in combination with the economic and environmental impact.The results have important guiding significance for realizing efficient,energy-saving,and green azeotropic separation systems in industry.

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.

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.

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.

Application of the Chemical-Looping Concept for Azoetrope Separation

The need for the separation of azeotropic mixtures for the production of high-end chemicals and resource recovery has spurred significant research into the development of new separation methods in the chemical industry.In this paper,a green and sustainable method for azeotrope separation is proposed based on a chemical-looping concept with the help of reversible-reaction-assisted distillation.The central concept in the chemical-looping separation(CLS)method is the selection of a reactant that can react with the azeotrope components and can also be recycled by the reverse reaction to close the loop and achieve cyclic azeotrope separation.This paper aims to provide an informative perspective on the fundamental theory and applications of the CLS method based on the separation principle,reactant selection,and case analysis,for example,the separation of alkenes,alkane,aromatics,and polyol products.In summary,we provide guidance and references for chemical separation process intensification in product refining and separation from azeotropic systems for the development of a more sustainable chemical industry.

Design and control of fraction cutting for the separation of mixed alcohols from the Fischer-Tropsch aqueous by-products

Since the minimum-boiling azeotropes of C2-C8 alcohols with water and high-water content(up to 95%(mass))in the Fischer-Tropsch aqueous by-products,the separation is energy-intensive and challenging.The energy-saving strategy for the complete separation of the Fischer-Tropsch aqueous by-products has received massive attention in recent decades.In this study,a stripper-sidestream decanter process is proposed by exploiting homogeneous azeotropes(C2-C3 alcohols-water)and heterogeneous azeotropes(C4-C8 alcohols-water).The introduction of the stripping column for pre-dehydration avoids the revaporization of the mixture,and energy carried by the overhead vapor is conserved instead of being removed in a condenser.The precise fraction cutting of C1-C3 alcohol-water mixture,C4-C8 alcohols,and water is realized by the sidestream distillation column.The C4-C8 alcohols rich mixture withdrawn from the sidestream flows into the decanter to break the distillation boundary,where the organic phase returns to the sidestream distillation column to obtain the dehydrated C4-C8 alcohols,and the aqueous phase enters the stripping column.Steady-state optimization based on total annual cost(TAC)minimization shows that the stripper-sidestream decanter process reduces TAC by 17.00%and saves energy by 21.27%compared with the conventional three-column distillation process.Further,a control structure of the process is established,and dynamic simulations show that the control structure combining a differential controller with a low-selector exhibits robust co ntrol.This study provides a novel design scheme and deepens the insights into the efficient separation of aqueous by-products of the Fischer-Tropsch synthesis.

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.

QUANTITATIVE EVALUATION OF ARRANGEMENT OF MONOMERS IN LINEAR BINARY COPOLYMERS USING A MONTE CARLO SIMULATION METHOD

A Monte Carlo method was used to take thorough account of the influences of different reactivity ratios and initial feed compositions on copolymer microstructure.The model proves the lack of azeotropic behavior in systems in which r_A>1 and r_B<1 or vice versa;it is also able to calculate the drift in the copolymer properties:copolymer composition,and randomness parameter.Moreover,for each reactivity ratio pair given,there is a unique reaction conversion,at which macromolecules produced inherit their ...

SYNTHESES OF PHOTOCHROMIC PIGMENTS

Photochromism is a phenomenon that a compound undergoes a reversible color change with the change of the wavelength of the irradiating light. Many photochromic compounds have been used in textiles as photochromic pigments.In this paper, some special techniques are used to prepare a photochromic compound of spirooxazines with an improved yield. Another photochromic spirooxazine with a sulfonate group which is soluble in water is also successfully synthesized. Tests are also conducted to find that they both display good photochromism in proper states.

Comparison of Extractive Distillation and Pressure-Swing Distillation for Methanol and Acetonitrile Separation

In the present work,a comparative study of the extractive distillation and pressure swing distillation for methanol-acetonitrile separation is performed for the first time.Different separation alternatives,including the conventional extractive distillation,the extractive distillation with vapor or liquid side-stream,the pressure-swing distillation with or without full heat integration,and the heat-pump assisted pressure-swing distillation are rigorously simulated and optimized based on the minimum total annual cost(TAC)via the sequential iterative strategy.The results show that TAC and CO2 emission of the new extractive distillation with vapor side-stream(Vapor-SED)are similar to those of the extractive distillation with liquid side-stream(Liquid-SED).Furthermore,the Vapor-SED and Liquid-SED can achieve 30.01%and 30.56%reduction in TAC and 23.32%and 23.49%reduction in CO2 emission,respectively,over the most competitive fully heat-integrated PSD configuration.Hence,the extractive distillation with vapor or liquid side-stream appears to be a better option economically and environmentally for the separation of methanol and acetonitrile.

Pressure Swing Distillation for Separation of Ethyl Acetate and Ethanol in Sub-plateau Region

The pressure swing distillation(PSD)process for separation of ethyl acetate and ethanol mixture in subplateau region was simulated.The pressure of low-pressure column was set at 0.086 MPa,which is in accordance with the atmospheric pressure in the Yunnan-Guizhou region,while the pressure of high-pressure column was determined as 0.304 MPa.Various design parameters,including the plate number,the reflux ratio,and the feeding positions,were optimized,while taking into consideration the total annual cost(TAC).Furthermore,based on the general PSD,the partially heatintegrated pressure swing distillation(PHIPSD)process and the fully heat-integrated pressure swing distillation(FHIPSD)process were also studied.The processes with heat integration showed lower capital cost and lower energy cost,and TACs of the PHIPSD and FHIPSD decreased to 377.21×103$/a and 371.66×103$/a,respectively.Compared with the non-heat integrated process,TACs of the PHIPSD and FHIPSD could be reduced by 27.82%and 28.89%,respectively.The results showed that the FHIPSD process could effectively separate the ethyl acetate-ethanol mixture,and it was more economical and reasonable.This work can provide some technical references for the separation of such azeotropes in the sub-plateau region.

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

１ＩＮＴＲＯＤＵＣＴＩＯＮＩｔｉｓｗｅｌｋｎｏｗｎｔｈａｔｓｉｎｔｅｒｉｎｇｔｅｍｐｅｒａｔｕｒｅｗｉｌｂｅｇｒｅａｔｌｙｄｅｃｒｅａｓｅｄｄｕｅｔｏｐｒｅｐａｒａｔｉｏｎｏｆｕｌｔｒａｆｉｎｅａｎｄｈｏｍｏｇｅｎｅｏｕｓｐｏｗｄｅｒｓ．Ａｓａｒｅ...

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: azeotropic 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 0.35 Ω·cm2 for the cathode synthesized by azeotropic distillation route, which is much lower than sol-gel (1.5 Ω·cm2) and solid state reaction (2.3 Ω·cm2) at 800 ℃.

Preparation of Liquor Flavoring from Yellow Water Based on Water Absorbent Resin

[Objective] This study was conducted to extract the scarce natural liquor flavorings desired by many liquor factories from yellow water. [Method] Strong water absorbent resin was used to absorb moisture from the yellow water in order to concentrate it into dense yellow water at first, followed by azcotropic dis- tillation of the previously concentrated yellow water, and then, catalytic esterification was performed to the remaining liquid after the distillation. [ Results] The 7. 066 7 fractions of concentrated yellow water with 56.7% ethanol could be obtained after the treatment of 100 fractions of yellow water with strong water absorbent resin. Azeotrope of 0.432 8 fraction of natural acetaldehyde, 0. 269 4 fraction of ethyl formate and methyl alcohol, 0. 975 0 fraction of ethyl acetate and methyl alco- hol could be obtained after the azeotropic distillation per 100 fractions of concentrated yellow water. After the addition of CaC12, O. 220 7 fraction of ethyl formate and 0. 514 2 fraction of ethyl acetate could be obtained after distillation of the azeotrope. Finally, 92. 094 8 fractions of esterification liquid with 38 kinds of flavor- ing compound could be obtained after catalytic esterification of 100 fractions of concentrated yellow water, and the content of ethyl acetate, ethyl propionate, ethyl- butyrate, ethyl valerate, ethyl lactate and ethyl bexanoate were as much as 142.9, 22.2, 54.2, 3.3,75.4 and 158.9 g/L, respectively. [ Conclusion] Top-grade Luzhou-flavor liquor could be made by mixing 6.5 fractions of common liquor with acetaldehyde, ethyl formate, ethyl acetate and esterification liquid which were ob- tained from 1 fraction of yellow water. Therefore, the yellow water has a great recycling value, and it tells us that the technique of extracting liquor flavorings from yellow water has tremendous market value.

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.

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.