Liquid–liquid equilibrium extraction of ethanol with mixed solvent for bioethanol concentration

The extraction of ethanol with the solvents of aldehydes mixed with m-xylene was studied for the bioethanol concentration process.Furfural and benzaldehyde were selected as extraction solvents,with which the solubility of water is small,expecting large distribution coefficient of ethanol.The liquid–liquid two-phase region was the largest with m-xylene solvent,followed by benzaldehyde and furfural.The region of two liquid–liquid phase became larger with the mixed solvent of m-xylene and furfural than that with furfural solvent.The NRTL model was applied to the ethanol–water–furfural–m-xylene system,and the model could well express the liquid–liquid equilibrium of the system.For any solvent used in this study,the separation selectivity of ethanol relative to water decreased as the distribution coefficient of ethanol increased.The separation selectivity with m-xylene was the largest among the employed solvents,but the distribution coefficient was the smallest.The solvent mixture of furfural and m-xylene showed relatively high distribution coefficient of ethanol and separation selectivity,even in the higher mass fraction of m-xylene in the solvent phase.The ethanol extraction with a countercurrent multistage extractor by a continuous operation was simulated to evaluate the extraction performance.The ethanol content could be concentrated in the extract phase with relatively small number of extraction stages but low yield of ethanol was obtained.     

Preface

<正>Every three years the world's leaders in solvent extraction get together at the International Solvent Extraction Conference and in2014 it was held in Wurzburg in Germany.The following are 9 papers that were picked out that show an overview of the work presented and provide an update on some of the research being undertaken in solvent extraction today.For me the trend to environmentally sustainable bio derived solvents is a key for     

萃取体系滴内和两相阻力控制的单液滴传质实验和数值模拟研究

Numerical simulation of transient mass transfer to a single drop controlled by the internal resistance or by the resistance in both phases was mathematically formulated and simulated in a boundary-fitted orthogonal coordinate system. The simulated results on the transient mass transfer dominated by the internal resistance are in good agreement with the Newman and Kronig-Brink models for drops with low Reynolds number. When the drop Reynolds number is up to 200, the mass transfer coefficient from numerical simulation is very low as compared with the Handlos-Baron model. The cases with mass transfer resistance residing in both the continuous and drop phases were simulated successfully and compared with the experimental data in three extraction systems recommended by European Confederation of Chemical Engineering (EFCE). For single drops with Re ＜ 200, the numerically predicted values of the extraction fraction and overall mass transfer coefficient are in reasonable coincidence with the experimental data. It is concluded that the numerical simulation can be resorted in some cases of solvent extraction for conducting numerical experiments and parametric study. Nevertheless, for better resolution as higher Reynolds number drops are simulated, more sophisticated techniques should be developed and incorporated to deal with the large deformation and transient shape oscillation as well as possible Marangoni effect.     

Separation of light hydrocarbons with ionic liquids: A review

Light hydrocarbons(C_1–C_4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.     

Jatropha curcas L. oil extracted by switchable solvent N,N-dimethylcyclohexylamine for biodiesel production

Biodiesel, which is a renewable and environmentally friendly fuel, has been studied widely to help remedy increasing environmental problems. One of the key processes of biodiesel production is oil extraction from oilseed materials. Switchable solvents can reversibly change from molecular to ionic solvents under atmospheric CO_2,and can be used for oil extraction. N, N-dimethylcyclohexylamine(DMCHA), a switchable solvent, was used to extract oil from Jatropha curcas L. oil seeds to produce biodiesel. The appropriate extraction conditions were:1:2 ratio of seed mass to DMCHA volume, 0.3–1 mm particle size, 200 r·min-1agitation speed, 60 min extraction time, and 30 °C extraction temperature. The extraction ratio was about 83%. This solvent extracted the oil more efficiently than hexane, and is much less volatile. By bubbling CO_2 under 1 atm and 25 °C for 5 h, the oil was separated, and DMCHA was recovered after releasing CO_2 by bubbling N_2 under 1 atm and 60 °C for 2 h. The residual solvent content in oil was about 1.7%. Selectivity of DMCHA was evaluated by detecting the protein and sugar content in oil. Using the oil with residual solvent to conduct transesterification process, the oil conversion ratio was approximately 99.5%.     

SOME THEORETICAL PROBLEMS OF ANIONIC POLYMERIZATION OF BUTADIENE——A Study on the Association Degree of n-BuLi and Polybutadienyl-Li

This paper determined the association degree of n-BuLi and polybutadinyllithium(PBLi)by UV spec-trometry and viscometry.The experimental results of UV spectrometric analysis showed that the associationdegree of n-BuLi as well as PBLi is dependent mainly on their concentration in solutions;there may be specieswith three and two degrees of association in cyclohexane solvent respectively for n-BuLi and PBLi,i.e.the asso-ciation degree for the former is equal to 2,4 and 6;and for the latter it equals to 2 and 4.Similarly,the experi-mental results obtained by viscometric measurement showed that the average association degree N of PBLiin cyclohexane changed from 2 to 4 with increasing of its concentration in solution and decreased with addi-tion of a small amount of polar additive into the above mentioned system.Furthermore,in pure polar solvent,such as dimethoxyethane(DME),tetrahydrofuran(THF)or dioxane(DOX),PBLi is completely dissociatedinto monomeric species;however,in pure diethyl ether,due to its weak polarity a part of associated species stillcan be found.Generally speaking,all of the above results were consistent with the results of kinetic studies in-vestigated by us before.     

散相液滴在搅拌萃取塔内的停留时间分布

A resident time model is proposed to evaluate the performance of agitated extraction columns. In this model, the resident time of dispersed drops is simulated with the discrete phase modeling, where the continuous phase and the dispersed phase （drops） are described by the single-phase Navier-Stokes （turbulence） model and Lagrangian model, respectively. The interaction of dispersed phase and continuous phase is neglected for the low concentration of drop in the cases studied. The statistical parameters of drops （the average resident time and standard deviation） under different operation conditions are computed for four columns. The relation of the above statistical parameters with the performance of columns is discussed and the criterions for an optimal compartment are outlined. Our results indicate that the resident time model is useful to evaluate the performance and optimize the design of extraction columns.     

A NEW PROCESS FOR THE EXTRACTION OF PENICILLIN G FROM THE FILTRATE OF FERMENTATION BROTH WITH TBP IN BUTYL ACETATE

The mixture of neutral phosphorus esters and butyl acetate (BA) can be used, as the extractant for the extraction of penicillin G. The extraction equilibrium pH can be increased to pH3—4 due to the stronger extraction capability of the solvent mixture, instead of pH1.8—2.2 with butyl acetate as solvent. The experimental results indicate that the total recovery of penicillin G can reach 96.6% with the new extraction process, which is 5—6% higher than that obtained with the traditional process using BA as solvent at pH1.8—2.2.     

全氟壬烯氟两相体系及其在酯化反应中的应用

Some apolar organic solvents is miscible with perfluorous nonene to form fluorous biphase systems.Perfluorous nonene could be used as a green solvent in equimolar esterification of carboxylic acids with alcohols without removal of water or ester formed. Perfluorous nonene made the esterification equilibrium to move right and the yields of esterification to enhance in different degrees as compared with that in the absence of perfluorous nonene. After esterification perfluorous nonene is easy to be recovered and recycled.     

Review on current advances,future challenges and consideration issues for post-combustion CO2 capture using amine-based absorbents☆

Among the current technologies for post-combustion CO2 capture, amine-based chemical absorption appears to be the most technologically mature and commercial y viable method. This review highlights the opportunities and challenges in post-combustion CO2 capture using amine-based chemical absorption technologies. In addi-tion, this review provides current types and emerging trends for chemical solvents. The issues and performance of amine solvents are reviewed and addressed in terms of thermodynamics, kinetics, mass transfer, regeneration and solvent management. This review also looks at emerging and future trends in post-combustion CO2 capture using chemical solvents in the near to mid-term.     

Deep Eutectic Solvent as Green Solvent in Extraction of Biological Macromolecules: A Review

Greater awareness of environmental sustainability has driven many industries to transition from using synthetic organic solvents to greener solvents in their manufacturing. Deep eutectic solvents (DESs) have emerged as a highly promising category of green solvents with well-demonstrated and wide-ranging applications, including their use as a solvent in extraction of small-molecule bioactive compounds for food and pharmaceutical applications. The use of DES as an extraction solvent of biological macromolecules, on the other hand, has not been as extensively studied. Thereby, the feasibility of employing DES for biomacromolecule extraction has not been well elucidated. To bridge this gap, this review provides an overview of DES with an emphasis on its unique physicochemical properties that make it an attractive green solvent (e.g., non-toxicity, biodegradability, ease of preparation, renewable, tailorable properties). Recent advances in DES extraction of three classes of biomacromolecules—i.e., proteins, carbohydrates, and lipids—were discussed and future research needs were identified. The importance of DES’s properties—particularly its viscosity, polarity, molar ratio of DES components, and water addition—on the DES extraction’s performance were discussed. Not unlike the findings from DES extraction of bioactive small molecules, DES extraction of biomacromolecules was concluded to be generally superior to extraction using synthetic organic solvents.     

低共熔溶剂在车用燃料脱硫中的研究进展

低共熔溶剂作为近十年来迅速发展的一类新型绿色溶剂,不仅具备离子液体的优点,而且原料价廉易得、合成条件简单、萃取脱硫效果好,已成为继离子液体用于车用燃料脱硫研究之后又一新的研究热点。本文根据合成低共熔溶剂的盐与氢键供体（或水合盐）的不同,对用于车用燃料脱硫的低共熔溶剂进行了分类总结,简述了低共熔溶剂的物化性质,介绍了低共熔溶剂用于车用燃料脱硫的方法及研究进展,对比了低共熔溶剂对不同含硫化合物的脱除效果,归纳了低共熔溶剂的萃取脱硫和氧化萃取脱硫机理。最后针对低共熔溶剂用于车用燃料脱硫中存在的选择性低、循环再生等关键问题,指出了其研究发展方向应是通过开发具有萃取脱硫高选择性的低共熔溶剂以及寻找新型绿色环保的低共熔溶剂脱硫方法来实现深度脱硫。     

Canola Oil with High Antioxidant Content Obtained by Combining Emerging Technologies: Microwave,Ultrasound, and a Green Solvent

In this work, the ultrasound‐assisted extraction (UAE) of canola oil from canola seeds pretreated with microwaves using ethanol 99% as solvent is studied. Different process parameters are evaluated, such as extraction time, temperature, solid:solvent ratio, and ultrasound amplitude, optimizing the process using response surface methodology. Under optimum conditions, the extraction time is decreased by up to 75% with respect to conventional extractions, obtaining an oil with a higher content of total tocopherols and canolol, and with oxidation indexes within the established standard limits. The addition of a microwave pretreatment to the UAE with ethanol 99% shows a synergic effect between both processes, improving the oil yield. The results obtained in this study show the potential of the use of UAE for the extraction of canola oil using a green solvent, reducing processing times, environmental pollution, and achieving an oil of high quality and antioxidant concentration. Practical Application: The industrial use of petroleum‐derived solvents such as hexane has problems concerning sustainability, environment, and safety. In recent years, the use of “green” solvents for the extraction of vegetable oils began to be studied; however, it is necessary to develop stages that allow improving the extraction process by increasing the yield, reducing the processing times, and optimizing the oil quality. In this sense, ultrasound allows to shorten the extraction times while microwave pretreatments applied to canola seeds generate an increase in the concentration of antioxidants in the oil, facilitating the implementation of a “green” process in the industrial production.     

Green solvents for green technologies

In many industrial processes, large quantities of volatile and flammable organic solvents are used in various reaction systems and separation steps defining a major part of the environmental and economic performance of a process. Accordingly, a growing area of research in the development of green technologies is devoted to designing new, environment‐friendly and tunable solvents the use of which would meet both technological and economic demands. Among proposed solvents, room temperature ionic liquids, supercritical and subcritical fluids and solvents from natural and renewable sources stand out as the most promising approaches for current solvent innovation. A brief overview of up‐to‐date knowledge regarding these solvents is presented herein, with special emphasis on their properties, applications and further perspectives as truly green industrial solvents. © 2015 Society of Chemical Industry     

Designing a biocatalytic process involving deep eutectic solvents

During the last decade, deep eutectic solvents (DESs) have emerged as a promising alternative to traditional organic solvents, from both environmental and technological perspectives. The number of structural combinations encompassed by DESs is tremendous; thus, it is possible to design an optimal DES for each specific enzymatic reaction system. In (bio)catalytic processes, a DES can serve as solvent/co‐solvent, as an extractive reagent for an enzymatic product, and as a pretreatment solvent of enzymatic biomass. To date, hydrolases are the most studied enzymes in DESs, which is not surprising given that lipases are the most important industrial enzymes. At the same time, there are a limited number of papers dealing with synthetic reactions in DESs involving other hydrolytic enzymes (epoxide hydrolases, phospholipase, proteases and haloalkane dehalogenases), lyases, and dehydrogenases (as a part of the whole Saccharomyces cerevisae and Escherichia coli cell biocatalysis). When designing efficient biocatalytic processes involving DESs, independent of the reaction type and enzyme used, the following steps should be included: (i) preparation and characterisation of the DES, (ii) screening of the DES for optimal enzyme performance, (iii) selection and optimisation of the biocatalytic protocol, and (iv) recovery of the product/DES and DES recycling with possible scale‐up. In this paper, we will present some practical aspects that we experienced while working with these solvents, together with some major observations that are available in the literature. © 2020 Society of Chemical Industry     

Hexane and heptane as extraction solvents for cottonseed: A laboratory-scale study

For many years, commercial-grade hexane has been the preferred solvent for extracting oil from cottonseed. Recent environmental and health concerns about hexane may limit the use of this solvent; therefore, the need for a replacement solvent has become an important issue. Heptane is similar to hexane, but does not have the environmental and health concerns associated with the latter. On a laboratory scale, delinted, dehulled, ground cottonseed was extracted with hexane and heptane. The solvent-to-meal ratio was 10:1 (vol/wt). The yield and quality of the oil and meal extracted by heptane were similar to that extracted by hexane. Extraction temperature was higher for heptane than for hexane. A higher temperature and a longer time were required to desolventize miscella from the heptane extraction than from the hexane extraction. Based on these studies, heptane offers a potential alternative to hexane for extracting oil from cottonseed.     

脱漆剂的研究进展与展望

简述了传统化学脱漆剂，包括热碱溶液脱漆剂，酸性脱漆剂和有机溶剂脱漆剂。重点评述了CH2Cl2型有机溶剂脱漆剂配方及其改进配方，并针对其存在的高挥发性、腐蚀性及毒性等缺点，综述了生态型脱漆剂的研究进展。同时指出，添加各种挥发抑制剂、腐蚀抑制剂、增稠剂和分散剂等可降低氯化溶剂类脱漆剂的危害，但不能作为脱漆剂的研究方向。展望了选用非挥发性的酯及芳香化合物作为替代品，N-烷基吡咯烷酮类物质作为配方助剂以及开发乳化体形态的脱漆剂等手段将是脱漆剂配方研究的未来发展方向。     

克拉玛依油砂溶剂萃取分离实验研究

以克拉玛依油砂为实验对象,考察石油醚、环己烷、正戊烷、正庚烷、甲苯、CS2及复合溶剂EOSA萃取分离油砂沥青的效果,确定EOSA为最佳萃取溶剂。研究了温度、溶剂用量、时间对EOSA萃取分离油砂沥青收率的影响。结果表明,在萃取温度30℃、剂砂比2 mL/g条件下萃取30 min,油砂沥青的收率可达95%以上。再生实验结果表明,在60~80℃条件下,溶剂回收率超过99%。该工艺具有无水参与、零排放、低能耗、高收率等优点。     

低共熔溶剂在电池和电催化中的应用

绿色且高效的电池和电催化反应是可持续发展的基本要求,其关键因素之一在于选择能提高效率的绿色电解质和合成高效电极材料的绿色溶剂。低共熔溶剂(DESs)是一种新型环境友好的电解质和溶剂。与传统的溶剂和电解质(如离子液体、水、超临界二氧化碳)相比,DESs具有合成简便、价格低廉、可设计等优点,在电池和电催化领域有着广阔的应用前景。这方面的研究还处于起步阶段,未见有综述系统介绍。本综述内容包括以下几个部分。(1) DESs作为电池和电催化反应的电解质,其中电池包括太阳能电池、锂离子电池、钠电池、锌电池、铝电池、液流电池、超级电容器,电催化反应包括析氧反应、析氢反应、氧还原反应、全解水反应、氮气电催化反应、二氧化碳电还原反应;(2) DESs作为制备电池和电催化反应电极材料的溶剂;(3) DESs作为回收电极材料的溶剂;(4)结论和展望。     

Solvent treatment of coals: 1. Effects on microporosity at ambient temperature

The effects of extraction with thirteen solvents and three solvent mixtures at ambient temperature on the surface areas of three bituminous coals were investigated. The total surface area of each coal, measured by CO₂ at 298 K, was substantially increased by extraction with pyridine, ethylenediamine, methylpyrrolidinone and THF. The maximum surface area attained was nearly the same for the three coals—evidence for a similar, highly crosslinked macromolecular network type of structure in all three coals. Given enough time, the mixed solvents were also effective in increasing the total surface area when the ‘solubility parameter’ of the coal was equal to the ‘solubility parameter’ of the mixture. None of the solvents increased the surface area measured by nitrogen significantly, indicating that the pores opened by the extraction of soluble pore material were < 0.5 nm in size. All the effective solvents satisfied the donor and acceptor number requirements for extraction of pore material based on the donor-acceptor model of coal extraction.