Measurement and Correlation of Liquid–Liquid Equilibrium Data for Ethanol–Water–KF and Ethanol–Water–K2CO3 Systems

The liquid–liquid equilibrium data for two ternary systems, ethanol–water–KF and ethanol– water–K2CO3, were determined at 25℃. Experiments show that by adding KF or K2CO3 into the ethanol–water system two phases are formed: an ethanol-rich phase with negligible salt and a water-rich phase with negligible ethanol, thus water can be separated out easily. A mathematical calculation of the liquid–liquid equilibrium data was carried out with the Pitzer theory on water activity in the aqueous phase, and with the Wilson or NRTL or UNIQUAC equations for that in the ethanol phase, which is in good agreement with experimental data.     

Determination and correlation solubility of m-phenylenediamine in (methanol,ethanol, acetonitrile and water) and their binary solvents from 278.15 K to 313.15 K

In this study, the solubility of m-phenylenediamine in four pure solvents(methanol, ethanol, acetonitrile and water) and three binary solvent(methanol + water),(ethanol + water) and(acetonitrile + water) systems were determined in the temperature ranging from 278.15 K to 313.15 K by using the gravimetric method under atmospheric pressure. In the temperature range of 278.15 K to 313.15 K, the mole fraction solubility values of m-phenylenediamine in water, methanol, ethanol, and acetonitrile are 0.0093–0.1533, 0.1668–0.5589,0.1072–0.5356, and 0.1717–0.6438, respectively. At constant temperature and solvent composition, the mole fraction solubility of o-phenylenediamine in four pure solvents was increased as the following order:water b ethanol b methanol b acetonitrile; and in the three binary solvent mixtures could be ranked as follows:(ethanol + water) b(methanol + water) b(acetonitrile + water). The relationship between the experimental temperature and the solubility of m-phenylenediamine was revealed as follows: the solubility of mphenylenediamine in pure and binary solvents could be increased with the increase of temperature. The experimental values were correlated with the Jouyban–Acree model, van't Hoff–Jouyban–Acree model, modified Apelblat–Jouyban–Acree model, Sun model and Ma model. The standard dissolution enthalpy, standard dissolution entropy and the Gibbs energy were calculated based on the experimental solubility data. In the binary solvent mixtures, the dissolution of m-phenylenediamine could be an endothermic process. The solubility data,correlation equations and thermodynamic property obtained from this study would be invoked as basic data and models regarding the purification and crystallization process of m-phenylenediamine.     

Determination of Teicoplanin A2's Partition Coefficient in Different Liquid-Liquid Extraction Systems

Teicoplanin is one of the macrocyclic glycopeptide antibiotics, which is active against Gram-positive bacteria, and has attracted a lot of attention in the field of chiral separation recently. In this work, the partition coefficients and extraction ratio of teicoplanin in three different solvent systems were studied: conventional extraction, reactive extraction and reverse micelle extraction. With conventional solvent extraction, n-butanol demonstrated high partition coefficient for teicoplanin, but low extraction ratio because of its high solubility in water. Reactive extraction of teicoplanin showed the highest partition coefficient with almost 100% recovery in organic phase when tri-n-octylmethyl ammonium chloride (TOMAC) was used as extractant and pH value was above 5.0. A reverse micelle system, consisted of isooctane 10mmol-L-1 TOMAC 1% n-octanol, also offered high separation factor for teicoplanin. The results are beneficial for the design of teicoplanin separation and purification process.     

替考拉宁在不同液液萃取体系中分配系数的测定

Teicoplanin is one of the macrocyclic glycopeptide antibiotics, which is active against Gram-positive bacteria, and has attracted a lot of attention in the field of chiral separation recently. In this work, the partition coefficients and extraction ratio of teicoplanin in three different solvent systems were studied: conventional extraction, reactive extraction and reverse micelle extraction. With conventional solvent extraction, n-butanol demonstrated high partition coefficient for teicoplanin, but low extraction ratio because of its high solubility in water. Reactive extraction of teicoplanin showed the highest partition coefficient with almost 100% recovery in organic phase when tri-n-octylmethyl ammonium chloride (TOMAC) was used as extractant and pH value was above 5.0. A reverse micelle system, consisted of isooctane 10 mmol-L^-1 TOMAC -t-1% n-octanol, also offered high separation factor for teicoplanin. The results are beneficial for the design of teicoplanin separation and purification process.     

Measurements and thermodynamic modeling of liquid–liquid equilibria in ternary system 2-methoxy-2-methylpropane+p-cresol+water

Liquid–liquid equilibrium(LLE)data for the ternary system 2-methoxy-2-methylpropane(methyl tert-butyl ether)+ p-cresol + water was measured at atmospheric pressure and temperatures of 298.15 K and 313.15 K.From the distribution coefficients and selectivity,it was found that 2-methoxy-2-methylpropane is an efficient solvent to extract p-cresol from wastewater.The consistency of the experimental tie-line data was verified with the Hand and Bachman equations.These data were also correlated with the non-random two liquid(NRTL)and universal quasi-chemical correlation activity coefficient(UNIQUAC)models to yield binary interaction parameters for p-cresol extraction process evaluation.Both models agreed with experiments very well,yet the NRTL model showed even smaller average deviation than the UNIQUAC model.     

新型己内酰胺萃取剂的筛选和评价

Mixed solvent of 1-octanol and cyclohexane with 60% （by mass） 1-octanol content was selected as a new extractant for caprolactam extraction. Compared with benzene or toluene, the new extractant has larger extraction capacity and much lower toxicity. Although the extraction capacity of the new extractant is smaller than that of pure 1-octanol, 1-octanol solubility of the new extractant in aqueous phase is much smaller. Because of its physical properties of lower density, lower viscosity, and higher interfacial tension, the new extractant performed much better phase separation ability than pure 1-octanol. The new extractant showed certain selectivity when dealing with lactam oil. The mixed solvent of 1-octanol and cyclohexane with 60% （by mass） 1-octanol content is a promising extractant for caprolactam extraction.     

273.2K至293.2K之间D-葡萄糖、D-果糖和蔗糖在乙醇和水的混合溶剂中的固液平衡

Experimental data on the solubility of D-glucose, D-fructose and sucrose in the mixed solvents composed of water and ethanol from 273.2 to 293.2 K were determined. The solubility of D-glucose, D-fructose and sucrose decreased as the ethanol content increased in the mixed solvent. The solubility of D-glucose, D-fructose and sucrose decreased with decreasing equilibrium temperature. The modified UNIQUAC model, S-UNIFAC model and mS-UNIFAC model were applied to predict the solid-liquid equilibria. The prediction results were compared and discussed. Better prediction accuracy was generated using the modified UNIQUAC model.     

Determination of Vapor Pressures for Binary and Ternary Mixtures Containing Ionic Liquid 1-propyl-3-methylimidazolium Bromide

Vapor pressure values of binary systems water + ethanol, water + ionic liquid 1-propyl-3-methylimidazolium bromide ([PMIM][Br]), ethanol + [PMIM][Br] and ternary system water + ethanol + [PMIM][Br] at different temperatures were measured by using a modified boiling point method in various concentrations of (16.66%, 33.7%), (17.4%, 33.9%) and (16.5%, 32%) mass percent of ionic liquid, respectively. The experimental vapor pressures of solvent were well correlated by the Antoine-type equation, and the overall average absolute deviation (AAD) was found to be 0.39%. The experimental results for mixtures containing ionic liquid indicate that the vapor pressure of the solvents can be decreased noticeably to different extent due to the affinity difference between ionic liquid and solvent, which is similar to the salt effect of common inorganic salts. As a result, ionic liquid may find industrial applications in extractive distillations for the system with a low separation factor or even for an azeotropic mixture.     

一氧化碳在苯酚+乙醇中的溶解度测量和关联

The solubility of carbon monoxide in phenol＋ethanol mixed solvents at elevated pressures is reported in this article. The experimental results revealed the influence of pressure on the solubility of CO in phenol＋ethanol mixtures. These mixtures are a poorer solvent for carbon monoxide. The solubility of CO is a linear function of pressure, and the extended Henry＇s constants were presented at different concentrations of phenol. The cubic Soave-Redlich-Kwong equation of state was used to correlate the experimental gas liquid equilibrium data and to predict the solubility of CO. At the same time, the binary interaction parameters, kO, for CO-phenol, CO-ethanol and phenol-ethanol systems were estimated by fitting experimental GLE data at 303.15 K and at 2.0-9.0 MPa. Hence, a model was suggested for the solubility of CO in phenol＋ethanol mixed solvents. The agreement between experimental and calculated solubilities with the proposed model was rather satisfactory.     

含离子液体溴化1-丙基-3-甲基咪唑的二元和三元体系的蒸气压测定

Vapor pressure values of binary systems water ＋ ethanol, water ＋ ionic liquid 1-propyl-3- methylimidazolium bromide （[PMIM] [Br]）, ethanol ＋ [PMIM] [Br] and ternary system water ＋ ethanol ＋ [PMIM] [Br] at different temperatures were measured by using a modified boiling point method in various concentrations of （16.66%, 33.7%）, （17.4%, 33.9%） and （16.5%, 32%） mass percent of ionic liquid, respectively. The experimental vapor pressures of solvent were well correlated by the Antoine-type equation, and the overall average absolute deviation （AAD） was found to be 0.39%. The experimental results for mixtures containing ionic liquid indicate that the vapor pressure of the solvents can be decreased noticeably to different extent due to the affinity difference between ionic liquid and solvent, which is similar to the salt effect of common inorganic salts. As a result, ionic liquid may find industrial applications in extractive distillations for the system with a low separation factor or even for an azeotropic mixture.     

Separation of aromatic components from light cycle oil by solvent extraction

To improve the versatility of light cycle oil (LCO), separation of aromatic compounds from LCO by solvent extraction was investigated. LCO was analyzed to identify 35 components: 19 aromatics and 16 alkanes. The batch liquid–liquid equilibrium extraction of LCO was performed using furfural, sulfolane, and methanol as extraction solvents. In each solvent, the aromatics present in LCO were selectively extracted relative to the alkanes. The separation selectivities of aromatics relative to alkanes were larger in sulfolane than in the other solvents. Among the aromatic components, di- and tricyclic compounds were selectively extracted relative to the monocyclic ones.     

错流萃取分离二乙氧基甲烷与乙醇的模拟及实验研究

设计了二乙氧基甲烷和乙醇水溶液的错流萃取分离工艺,实验确定了以多元醇和水为复合萃取溶剂分离二乙氧基甲烷-乙醇体系适宜的比例.采用相分配系数法对该过程进行了模拟计算及萃取实验.实验及模拟结果表明:当原料与2种溶剂进料体积比为1:1:1时,经过3级错流萃取分离后,萃余相中二乙氧基甲烷质量分数可达99.9%,收率达99.0%...     

Separation of Aromatic Solvents from the Reformate Fraction of an Oil Refining Process using Extraction by a Designed Ionic Liquid

Separation of aromatic solvents, from mixtures containing aliphatic solvents as the major fraction, is important, inter alia, for its reuse in industrial processes. This report deals with the use of a designed and synthesized ionic liquid (N-butyl-N-methyl-2-oxopyrrolidonium bromide) for the separation of benzene, toluene, ethylbenzene, and xylene (BTEX), including all the isomers of xylene. For comparison purposes, a previously-used ionic liquid (1-ethyl-3-methylimidazolium ethyl sulphate) was also synthesized and used. The experimental parameters established for the separation/extraction of the mixed standard of BTEX were applied to the separation/extraction of the components of BTEX from the reformate fraction of an oil refining process. The method was tested for BTEX components varying in concentration from 0.5 to 10%. The results show that the new ionic liquid gives higher extraction efficiency than the one used in a previous project. The results are as good as that obtained by a local oil refinery which used a conventional solvent. Furthermore, the results reveal a general increase in percentages extracted in the following order: m-xylene < p-xylene ? o-xylene < ethyl benzene < toluene < benzene.     

以混合溶剂精制润滑油

以混合溶剂精制润滑油杨卓如黄洪杨晓燕兰仁华陈焕钦（华南理工大学化工学院，广州５１０６４１）关键词润滑油溶剂精制糠醛１前言目前，我国在润滑油精制过程中仍主要用糠醛作为溶剂。糠醛精制装置占溶剂精制装置的７５．８％，其精制工艺已趋于成熟。预计糠醛精制仍将...     

NMP和糠醛精制减五线脱蜡油模拟连续抽提试验研究

用沈北、大庆混合油减五线脱蜡油为原料进行了NMP溶剂和糠醛溶剂精制的对比研究.在单级抽提试验所确定出的NMP和糠醛精制最优操作条件基础之上,进行了两种溶剂的假三段抽提试验.对所得精制油进行了各项性质分析.在单级抽提实验所确定的适宜操作条件下,无论是NMP精制还是糠醛精制,假三段抽提与单级抽提相比在精制油质量变好的同时,精制油收率也略有提高.与糠醛假三段抽提实验相比,NMP 假三段溶剂精制的剂油比下降43％,收率基本不变.两者精制油质量基本相同.说明了NMP比糠醛有更好的精制效果.同样说明精制减五线脱蜡油时,NMP溶剂溶解能力和选择性均比糠醛溶剂好.     

Mechanism analysis of solvent selectivity and energy-saving optimization in vapor recompression-assisted extractive distillation for separation of binary azeotrope

Octane and p-xylene are common components in crude gasoline, so their separation process is very important in petroleum industry. The azeotrope and near azeotrope are often separated by extractive distillation in industry, which can realize the recovery and utilization of resources. In this work, the vapor–liquid equilibrium experiment was used to obtain the vapor–liquid equilibrium properties of the difficult separation system, and on this basis, the solvent extraction mechanism was studied. The mechanism of solvent separation plays a guiding role in selecting suitable solvents for industrial separation. The interaction energy, bond length and charge density distribution of p-xylene with solvent are calculated by quantum chemistry method. The quantum chemistry calculation results and experiment results showed that N-formylmorpholine is the best solvent among the alternative solvents in the work. This work provides an effective and complete solvent screening process from phase equilibrium experiments to quantum chemical calculation. An extractive distillation simulation process with N-formylmorpholine as solvent is designed to separate octane and p-xylene. In addition, the feasibility and effectiveness of the intensified vapor recompression assisted extraction distillation are also discussed. In the extractive distillation process, the vapor recompression-assisted extraction distillation process is globally optimal. Compared with basic process, the total annual cost can be reduced by 43.2%. This study provides theoretical guidance for extractive distillation separation technology and solvent selection.     

基于相图分析的润滑油糠醛精制工艺改进

针对原料油中饱和分与芳香分分离精度低导致糠醛精制工艺抽余油收率低、抽出油质量差的问题,提出基于热力学相图分析的糠醛精制工艺的改进策略。基于虚拟组分法简化润滑油组分为饱和分、芳香分和极性分,采用NRTL模型预测不同温度下的相平衡数据,分析抽提过程液液相平衡关系及操作条件对萃取过程的影响规律,发现温度是影响平衡组成和传质效率的关键因素。基于相图对萃取过程的分析,通过设计多级抽出液回收系统,多温度梯级分离抽出液,解决抽提塔在较低温度下难以操作的问题。结合实际糠醛精制装置进行模拟计算,结果表明设置多级抽出液回收系统,抽提过程溶剂比及冷热公用工程量适当增加,抽余油收率较原工艺提高10%以上,抽出油质量极大改善,显著提升糠醛精制工艺的分离效率。     

Extraction of toluene and n-heptane mixture using ionic liquid Aliquat 336 and mathematical modeling for solvent selection

Liquid–liquid equilibrium data for the system consisting of toluene, n-heptane and Aliquat 336 ionic liquid was obtained at 303.15 K and atmospheric pressure. The values of distribution coefficient and selectivity were evaluated. Mathematical model relating distribution coefficient and dispersion, dipolar interaction and hydrogen bonding has been developed. Hansen’s solubility parameters were used to determine the parameters. The model was applied for various ionic liquids as solvents. The model predicted the trends similar to the trend reported in the literature. Thus model can predict better solvent for the given extraction application. This methodology has great potential to act as a knowledge-based framework to aid development of new tailor-made solvents. This will save cost and time in experimentation and analysis.     

A comparative study on solvents for separation of tert-amyl ethyl ether and ethanol mixtures. New experimental data for 1-ethyl-3-methyl imidazolium ethyl sulfate ionic liquid

Ionic liquids have potential applications on separation technologies, as solvents for liquid extraction, gas absorbers and others. In this work, the ability of 1-ethyl-3-methyl imidazolium ethyl sulfate, [emim][EtSO₄], to carry out the separation of tert-amyl ethyl ether and ethanol mixtures has been studied. New experimental LLE data for the ternary system are reported. Data correlation was done by means of the NRTL equation with satisfactory results (rmsd=0.429%). Extraction process was studied by means of solute distribution ratio and selectivity of the ionic liquid. Results were compared to other solvents from the literature. Solute distribution ratio for [emim][EtSO₄] was acceptable (higher than 1) and selectivity was better than for other solvents. Then, extraction processes were also simulated using conventional software and obtained results are shown for comparison. Best TAEE recovery was obtained with [emim][EtSO₄] and water.