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.

Comparison of Headspace Solid-Phase Microextraction with Simultaneous Steam Distillation Extraction for the Analysis of the Volatile Constituents in Chinese Apricot

Volatile constituents in fully mature fruits of apricot （Prunus armeniaca L.） cultivar Xinshiji were extracted using headspace solid-phase microextraction （HS-SPME） and simultaneous steam distillation extraction （SSDE） and then analyzed using capillary gas chromatography and gas chromatography-mass spectrometry. A total of 70 components were identified by HSSPME, including 20 esters, 19 hydrocarbons, 5 alcohols, 5 ketones, 4 acids, 4 lactones, 3 aldehydes, and 10 miscellaneous components, with the esters being the dominant constituent. On the basis of the odor unit values, it is believed that the following compounds probably contributed to the fresh apricot odor： hexyl acetate, β-ionone, butyl acetate, （E）-2-hexenal, linalool, limonene, γ-decalactone, and hexanal. A total of 49 components were also detected by SSDE, including 13 hydrocarbons, 9 alcohols, 7 aldehydes, 9 esters, 4 ketones, 4 lactones, 2 acids, and 1 miscellaneous component, of which the monoterpene alcohols were the dominant constituents. It could be judged from the odor unit values that the following compounds were the major contributors to boiled apricot aroma： β-ionone, linalool, hexyl acetate, γ-dodecalactone, γ- decalactone, （E）-2-hexenal, hexanal, γ-octalactone, phenylacetaldehyde, butyl acetate, limonene, α-terpineol, and δ-decalactone. The results show that HS-SPME is a simple, rapid, and solvent-free method, which is an alternative to the classical SSDE.

Comparison of simultaneous distillation extraction and solid-phase micro-extraction for determination of volatile constituents in tobacco flavor

The volatile and semi-volatile components in tobacco flavor additives were extracted by both simultaneous distillation extraction and solid-phase micro-extraction. Extraction conditions for solid-phase micro-extraction were optimized with information theory. Then, detection were accomplished by gas chromatography-mass spectrometry. Characteristic of each method was compared. Qualitative analysis and quantitative analysis of 6# tobacco flavor sample were accomplished through both simultaneous distillation extraction and solid-phase micro-extraction. The experimental results show that solid-phase micro-extraction method is the first choice for qualitative analysis and simultaneous distillation extraction is another good selection for quantitative analysis. By means of simultaneous distillation extraction, 20 components are identified, accounting for 92.77% of the total peak areas. Through solid-phase micro-extraction, there are 17 components identified accounting for 91.49% of the total peak areas. The main aromatic components in 6# tobacco flavor sample are propanoic acid, 2-hydroxy-, ethyl ester, menthol and menthyl acetate. The presented method has been successfully used for quality control of tobacco flavor.

Comparison of volatile and semivolatile compounds from commercial cigarette by supercritical fluid extraction and simultaneous distillation extraction

Supercritical carbon dioxide fluid extraction (SFE) was studied as a rapid method for extraction of volatile and semivolatile compounds of Chinese commercial cigarettes. The method was compared with simultaneous distillation and extraction (SDE). Temperature and pressure for the SFE were optimized. The extracts obtained by the two methods showed different characters in composition and represented differently the flavor characteristics of tobacco; compared to SDE, SFE can extract compounds within a shorter time and avoid the thermal degradation and solvent contamination of samples. The extracts by the two extraction methods are complementary for investigating the flavor characteristic of tobacco products.

Effectiveness and safety of early lens extraction during par plana vitrectomy for proliferative diabetes retinopathy with mild cataract:a randomized clinical trial

●AIM:To evaluate the effectiveness and safety of early lens extraction during pars plana vitrectomy(PPV)for proliferative diabetic retinopathy(PDR)compared to those of PPV with subsequent cataract surgery.●METHODS:This multicenter randomized controlled trial was conducted in three Chinese hospitals on patients with PDR,aged>45y,with mild cataracts.The participants were randomly assigned to the combined(PPV combined with simultaneously cataract surgery,i.e.,phacovitrectomy)or subsequent(PPV with subsequent cataract surgery 6mo later)group and followed up for 12mo.The primary outcome was the change in best-corrected visual acuity(BCVA)from baseline to 6mo,and the secondary outcomes included complication rates and medical expenses.●RESULTS:In total,129 patients with PDR were recruited and equally randomized(66 and 63 in the combined and subsequent groups respectively).The change in BCVA in the combined group[mean,36.90 letters;95%confidence interval(CI),30.35–43.45]was significantly better(adjusted difference,16.43;95%CI,8.77–24.08;P<0.001)than in the subsequent group(mean,22.40 letters;95%CI,15.55–29.24)6mo after the PPV,with no significant difference between the two groups at 12mo.The overall surgical risk of two sequential surgeries was significantly higher than that of the combined surgery for neovascular glaucoma(17.65%vs 3.77%,P=0.005).No significant differences were found in the photocoagulation spots,surgical time,and economic expenses between two groups.In the subsequent group,the duration of work incapacity(22.54±9.11d)was significantly longer(P<0.001)than that of the combined group(12.44±6.48d).●CONCLUSION:PDR patients aged over 45y with mild cataract can also benefit from early lens extraction during PPV with gratifying effectiveness,safety and convenience,compared to sequential surgeries.

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.

Comparison of Constituents and Insecticidal Activities of Essential Oil from Artemisia lavandulaefolia by Steam Distillation and Supercritical-CO_2 Fluid Extraction

Essential oil was extracted from Artemisia lavandulaefolia DC.by steam distillation（SD） and supercritical-CO2 fluid extraction（SFE）,respectively.The constituents of the essentil oils extracted with those two methods were analyzed by gas chromatography-mass spectrometry（GC-MS） and insecticidal activities of the essential oils were evaluated,then the results were compared to assess their biological activity.Thirty-one compounds were identified in the essential oil extracted by SD,and its main components were eucalyptol,α,α,4-trimethyl-3-cyclohexene-1-methanol and so on.Twenty-two compounds were identified for the essential oil extracted by SFE,and its main components were cyclodecene,n-hexadecanoic acid and so on.Six chemical compositions were all contained in the essential oils extracted by the two methods,i.e.,eucalyptol,α,α,4-trimethyl-3-cyclohexene-1-methanol,caryophyllene,[3aS-（3aα,3bβ,4β,7α,7aS）]-octahydro-7-methyl-3-methylene-4-（1-methylethyl）-1H-cyclopenta[1,3]cyclopropa-[1,2]benzene,nerolidol and（-）-Spathulenol.The fumigation toxicity of the essential oil obtained by means of SD to the adults of Sitophilus zeamais is significantly higher than that of the essential oil by means of SFE.The contact toxicity of the essential oil obtained by means of SFE to the adults of S.zeamais is higher than that of the essential oil obtained by means of SD,but the difference is not significant.

Enhanced extraction of essential oil from Cinnamomum cassia bark by ultrasound assisted hydrodistillation

Cinnamon essential oil with many bioactivities is an important raw material for the production of various chemicals,and the conventional hydrodistillation(HD)for cinnamon oil extraction always require a longer extraction time.In this work,ultrasound-assisted hydrodistillation extraction(UAHDE)technique was employed to enhance the extraction efficiency of essential oils from cinnamon barks.The parameters with significant effects on the essential oil extraction efficiency(ultrasound time,ultrasound power,extraction time,liquid–solid ratio)were optimized,and the proposed UAHDE was compared with the conventional HD extraction in terms of the extraction time,extraction yield,and physicochemical properties of extracted oils.Compared to the HD extraction,the UAHDE resulted in a shorter extraction time and a higher extraction yield.Using GC–MS analysis,the UAHDE provided more valuable essential oil with a high content of the vital trans-cinnamaldehyde compounds compared with the HD.Scanning electron micrograph(SEM)confirmed the efficiency of ultrasound irradiation for cinnamon oil extraction.In addition,the analysis of electric consumption and CO_(2) emission shows that the UAHDE process is a more economic and environment-friendly approach.Thus,UAHDE is an efficient and green technology for the cinnamon essential oil extraction,which could improve the quantity and quality of cinnamon oils.

Simultaneous Determination of Bisphenols and Alkylphenols in Water by Solid Phase Extraction and Ultra Performance Liquid Chromatography-tandem Mass Spectrometry

To establish an analytical method for determination of four bisphenols （BPA, BPB, BPF, and BPS） and two alkylphenols （4-n-OP, 4-n-NP） in water by ultra performance liquid chromatography- tandem mass spectrometry （UPLC/MS/MS）. The water samples were extracted and condensed with solid-phase extraction （SPE） using C18 cartridges and eluted by acetonitrile. Separation was carried out with Acquity BEH C8 column and detection were performed by UPLC/MS/MS. Quantification was calculated by using the internal standard BPA-d16 and 4-n-NP-d8. The linear correlation coefficients of these compounds in the range of 1.0-100.0μg/L were all over 0.999. The minimum detectable concentrations were 0.75-1.0 ng/L, and the recoveries ranged from 87.0% to 106.9%.

Active set truncated-Newton algorithm for simultaneous optimization of distillation column

An active set truncated-Newton algorithm (ASTNA) is proposed to solve the large-scale bound constrained sub-problems. The global convergence of the algorithm is obtained and two groups of numerical experiments are made for the various large-scale problems of varying size. The comparison results between ASTNA and the subspace limited memory quasi-Newton algorithm and between the modified augmented Lagrange multiplier methods combined with ASTNA and the modified barrier function method show the stability and effectiveness of ASTNA for simultaneous optimization of distillation column.

FEASIBILITY ANALYSIS OF SAFETY SIMULTANEOUS EXTRACTION OF COAL AND COALBED METHANE

Coalbed methane is of great value to extract and utilize in China, but the result of such research is not satisfied yet today.The paper analyzed the storage characteristics of coalbed methane, and then studied the behavior of coalbed methane using the key stratum theory of strata control.According to the features related to coalbed methane accumulations and delivery, the technique for safely simultaneous extraction of coal and coalbed methane is proposed, and benefit analysis is made too.

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.