Investigation of Three-liquid-phase Extraction Systems for Simultaneous Separation of Emodin and Rhein

Several three-liquid-phase extraction systems comprised of organic extractant,polymer and salt aqueous solution were applied to isolate and purify simulated herbal extract containing emodin and rhein.Some influential factors on the partitioning behaviors were studied.The results revealed that extractant type and solution pH value were crucial factors for improving the separation performance.The optimal separation results were obtained at pH 8.00 with methyl isobutyl ketone as the extractant,10%（ω） polyethylene glycol with the molecular weight 4000 Da,and 10%（ω） ammonium sulphate.Under the optimized conditions,95%emodin and 97%rhein were simultaneously extracted into the organic phase and polymer-rich phase from simulated herbal solution with the initial concentration of 100×l0^-6（ω）,respectively,and their separation factor of over 10000 was achieved.By adjusting pH value,back extraction rate of both emodin and rhein could be up to about 99%.With the assistance of molecular simulation program XLOGP3 and molecular orbital package,the possible mechanism of extraction was analyzed,and hydrophobic interaction and hydrogen-bonding interaction might be the major driving forces affecting the partitioning behaviors of emodin and rhein.     

Partition Behavior of Penicillin in Three-liquid-phase Extraction System

Partition behavior of penicillins G and V was studied in a novel three-liquid-phase extraction system, which is composed of butyl acetate (BA), polyethylene glycol (PEG), ammonia sulfate [(NH4)2SO4] and water (H2O). The main components in the top, middle and bottom phases are butyl acetate, polyethylene glycol aqueous solution and ammonia sulfate aqueous solution, respectively. Some parameters such as partition coefficients Di/j and mass fractions Ei of penicillins G and V were determined at the room temperature, respectively. Experimental efforts have been made to investigate the partition behavior of penicillin in the three-liquid-phase extraction system, including initial concentrations of phase-forming components [PEG and (NH4)2SO4], PEG molecular weight, pH, initial concentration of penicillin. The results indicated that penicillins G and V have the similar partition behavior. They preferentially distribute into the middle phase with the increase of initial concentration of phase-forming components and into the top phase with the decrease of pH, while partition coefficient Dm/b is hardly affected by pH value. The variation of PEG molecular weight has little effect on mass fractions of penicillin. The increase of initial concentration of penicillins G and V could lead to the increase of Dt/b, Dm/b and the decrease of Dt/m, while their mass fractions in all phases were almost independent on their initial concentrations.     

纤维素酶催化与三液相萃取偶联制备盾叶薯蓣皂苷元

利用三液相萃取与酶催化转化耦合技术对盾叶薯蓣中薯蓣皂苷进行水解,并分离提取薯蓣皂苷元。考察了几种甾体皂苷和水解下的葡萄糖在三液相中的分配、酶的分配以及酶活力在三液相体系中的保留情况,并对比了三液相、有机相、水相中纤维素酶催化转化与薯蓣皂苷元的生成情况。实验结果表明,正己烷/1,4-二氧六环/硫酸铵三液相体系能够满足酶催化和产物分离同步进行的要求,使薯蓣皂苷元分配在正己烷相,底物和酶保留在1,4-二氧六环相,大部分葡萄糖进入硫酸铵相,反应进行96h薯蓣皂苷元的得率为69.4%,比有机相、水相酶催化分别提高一倍和27.6倍,显示出耦合技术的明显优势。     

液液液三相萃取装置:操作参数对传质效率的影响(英文)

A new mixer-settler-mixer three chamber integrated extractor is proposed in this work for liquid-liquid-liquid three phase countercurrent and continuous extraction.Experiments revealed the influences of the structural design of the three-liquid-phase extractor and some key operational parameters on three-phase partition of two phenolic isomers,p-nitrophenol(p-NP) and o-nitrophenol(o-NP).The model three-liquid-phase extraction system used here is nonane(organic top-phase)-polyethylene glycol(PEG 2000)(polymer middle-phase)-(NH4)2SO4 aqueous solution(aqueous bottom-phase).It is indicated that agitating speed and retention time in three-phase mixer are key parameters to extraction fraction of nitrophenol.Dispersion band behavior is related to agitating in-tensity,and its occurrence does not affect the extraction fraction of target compounds.The present work highlights the possibility of a feasible approach of scaling up of the proposed three-phase extraction apparatus for future in-dustrial-aimed applications.     

由辣椒粉浸出液萃取辣椒碱

以市售干辣椒为原料、95%乙醇为浸出剂,实验研究了溶剂萃取法由辣椒粉浸出液中萃取纯化辣椒碱的工艺条件. 在模拟体系和实际体系中均以正己烷和乙酸丁酯为萃取剂,考察了pH值和有机相/水相体积比对辣椒碱收率的影响. 结果表明酸化萃取步骤为工艺控制步骤. 模拟体系中pH值为11、体积比为7:1时乙酸丁酯对辣椒碱的萃取收率均大于90%,表明以乙酸丁酯为萃取剂,可以提高辣椒碱的浓缩度. 实际体系萃取结果与模拟体系趋同,但约20%的辣椒碱不能被萃取. 实际体系优化的工艺条件为辣椒粉用量50 g,250 mL 95%乙醇2次浸出,辣椒碱收率为97.0%;浸出液浓缩为浸膏并溶解于NaOH溶液中,在pH值13, O/W体积比1:1时萃取,再用盐酸调节水相pH<11,O/W体积比为1:5时用乙酸丁酯萃取,辣椒碱的收率为浸出量的80%左右.     

溶剂萃取法分离氢化可的松和表氢化可的松

针对工业上现有结晶分离工艺的缺点,提出了分离氢化可的松及其光学异构体表氢化可的松的新方法——溶剂萃取法。实验发现,在常规醇类、酮类、酯类、醚类、氯代烃类和芳香烃等溶剂中,乙酸丁酯具有较好的萃取分离性能,以乙酸丁酯为萃取剂用溶剂萃取法分离氢化可的松粗品可获得纯度为９８％以上的氢化可的松,已达到工业生产水平。文中还研究了乙醇含量、温度、盐析效应和ｐＨ对分配的影响。     

Three-liquid-phase extraction and separation of V(V) and Cr(VI) from acidic leach solutions of high-chromium vanadium–titanium magnetite

A new method by liquid–liquid–liquid three phase system, consisting of acidified primary amine N1923(abbreviated as A-N1923), poly(ethylene glycol)(PEG) and (NH_4)_2SO_4 aqueous solution, was suggested for the separation and simultaneous extraction of V(V) and Cr(VI) from the acidic leach solutions of highchromium vanadium–titanium magnetite. Experimental results indicated that V(V) and Cr(VI) could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while Al(III)and other co-existing impurity ions, such as Si(IV), Fe(III), Ti(IV), Mg(II) and Ca(II) in acidic leach solutions,could be enriched in the(NH_4)_2SO_4 bottom aqueous phase. During the process for extraction and separation of V(V) and Cr(VI), almost all of impurity ions could be removed. The separation factors between V(V) and Cr(VI) could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered V(V) and Cr(VI) in the top phase and middle phase respectively were all above 90%.Various effects including aqueous p H, A-N1923 concentration, PEG added amount and(NH_4)_2SO_4 concentration on three-phase partitioning of V(V) and Cr(VI) were discussed. It was found that the partition of Cr(VI) into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of V(V) by A-N1923 resulted of anion exchange between NO_3~- and H_2V_(10)O_(28)~(-4). Stripping of V(V) and Cr(VI) from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NaNO_3 aqueous solutions and Na OH-((NH_4)_2SO_4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium–titanium magnetite.     

Impact of polyethylene glycol as additive on the formation and extraction behavior of ionic‐liquid based aqueous two‐phase system

Developing a novel Ionic‐liquid (IL) based aqueous two‐phase system (ATPS) with polyethylene glycol (PEG) as adjuvant for the separation of biomolecules is studied. This original work involves addition of various concentration of PEG (2000, 4000, and 6000 gr/mol) to 1‐butyl‐3‐methylimidazolium acetate+ potassium hydrogen phosphate ATPS to investigate their subsequent effect on phase diagrams and partitioning coefficient of α‐amylase. In another innovative aspect of this work, response surface methodology (RSM) based on three‐variable central composite design was employed to understand the effect of phase forming components on extraction studies of α‐amylase. The addition of small amount of PEG improved the partitioning coefficient of biomolecule. The effective excluded volume theory was applied to correlate the salting‐out ability. As a result, it can be stated that the proposed system can effectively be used in separation and purification studies instead of task specific ILs. © 2015 American Institute of Chemical Engineers AIChE J, 62: 264–274, 2016     

Extraction of Hydrocortisone from the Fermentation Liquor with Annular Centrifugal Contactors

Abstract

A continuous countercurrent extraction process for the recovery of hydrocortisone from the fermentation liquor has been developed with annular centrifugal contactors. When the hydrocortisone was extracted from the fermentation liquor with the butyl acetate, the distribution ratio increased with increase of the hydrocortisone concentration in the equilibrium aqueous phase. Both the laboratory tests and the plant tests have been finished with Φ20 mm and Φ230 mm annular centrifugal contactors respectively. In the laboratory tests, when the rotor speed was 3400～4200 r/min, the fermentation liquor flow was 30～50 mL/min and the phase ratio (V_O/V_A) was 0.36～0.50, the percent recovery of hydrocortisone was higher than 92%. In the plant tests, when the rotor speed was 2000 r/min, the fermentation liquor flow was 2000 L/h and the butyl acetate flow was 1000 L/h, the percent recovery of hydrocortisone was about 96.5～98%.     

Selective recovery of lithium from simulated brine using different organic synergist

The organic synergists, including Octanol, ethyl acetate(EA), butyl acetate(BA), methyl isobutyl ketone(MIBK),diisobutyl ketone(DIBK), N,N-bis(2-ethylhexyl) acetamide(N523) and 8-hydroxylquiolate, were added to the TBP–FeCl_3 extraction system to extract lithium from brine. The effects of concentration of organic synergist and total organic extractant, molar ratio of Fe/Li, phase ratio, counter-current extraction and the acidity of stripping agent on lithium extraction were investigated to optimize the extraction conditions. Under the optimize conditions, the results of counter-current extraction showed the mixed extraction system was the preponderance on the lithium extraction. Especially the separation of lithium in organic phase and aqueous phase and the separation mass ratio of Mg/Li increased greatly. An extraction mechanism was proposed based on the analysis of FT-IR spectra and Raman spectra.     

乳状液膜分离提取荷叶中3种生物碱

建立了用W/O型乳状液膜分离提取荷叶中3种生物碱——N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱的方法。通过对迁移时间、表面活性剂Span 80用量、载体D2EHPA浓度、油内比、乳水比和内水相盐酸浓度的优化,获得了高效的液膜体系,为:迁移时间2.5 min,表面活性剂Span 80的质量分数为3.0%,载体D2EHPA的浓度为0.01 mol/L,油内比为10∶6,乳水比为10∶60,内水相盐酸浓度为0.2 mol/L。在优化的实验条件下,对荷叶中3种生物碱N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱的萃取率分别达到了95.6%、100%和97.9%,相应的富集因子依次为8.73、8.50和8.04。说明该乳状液膜体系能够很好地分离提取荷叶中的N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱。     

Separation of Bromelain by Aqueous Two Phase Flotation

Aqueous two phase flotation (ATPF) system of polyethylene glycol (PEG) and potassium phosphate is studied for the separation and partial purification of bromelain from the pineapple fruit (Annanus comosus L. Merryl). The effect of PEG molecular weight (1500–20000), concentration of phase forming components (PEG 12–18% w/w and potassium phosphate 14–20% w/w), system pH, nitrogen flow rate, and flotation time were studied and optimum conditions for ATPF were obtained. At optimum conditions of the system, i.e., 14% w/w PEG 1500, 18% w/w potassium phosphate, 80 mL/min of nitrogen flow rate and pH 7, maximum yield of 91.47% and purification fold of 4.26 were obtained. ATPF was found to be an effective technique for the purification of bromelain from pineapple fruit with higher extraction yield and purification fold as compared to aqueous two phase extraction (ATPE).     

Interfacial Mass Transfer in the Reactive Extraction Process of Succinic Acid from Viscous Aqueous Solutions

The reactive extraction of succinic acid with TOA dissolved in butyl acetate from viscous aqueous solutions which simulate the rheological behavior of Actinobacillus succinogenes broths underlined the strong influence of viscosity and pH on interfacial mass flow, mass transfer driving force, and mass transfer coefficient. The magnitudes of these effects are attenuated by 1-octanol addition into the solvent phase, the interfacial mass transfer rate being accelerated for 1.2-3 times, depending on the apparent viscosity and the pH-value of the aqueous solution. The influences of the extraction parameters and mechanism have been included in a mathematical model adequate for the solute mass transfer coefficient from aqueous to organic phase.     

双水相萃取废液中成相物质聚乙二醇的回收利用

研究了双水相萃取废液中聚乙二醇的回收利用,旨在降低生产成本,减少COD排放,推动双水相萃取技术的工业应用进程。以聚乙二醇-硫酸铵[PEG-（NH4）2SO4]组成的双水相体系废液为原料,采用脱色、浓缩、洗涤除去杂质的工艺技术路线,确定了从双水相废液中回收成相聚合物PEG的最佳工艺（：1）利用H2O2法脱色,最佳脱色条件：H2O2浓度为6%,脱色温度为60℃,脱色时间为4 h,体系pH值为9.0,脱色率达到85%以上（;2）采取盐析法浓缩,最佳电解质种类为Na2SO4,最佳加入量为每10 mL废液3.0 g Na2SO4,此时PEG浓缩比为3.45,PEG损失率为0.31%。按照药用级PEG产品质量标准,对干燥后的回收物进行质量检测。结果表明：回收的PEG产品外观呈浅黄色蜡状,电导率为10.8μs/cm,凝固点为37～40℃,pH值（5%水溶液）为6.33,较纯品PEG无明显差异。     

TBP对LIX84由Cu2+-NH3-Cl——H2O系萃取铜及氨的影响

以Cu2+-NH3-Cl--H2O氨性溶液为被萃水相,在LIX84中添加磷酸三丁酯(TBP),考察了有机相中TBP浓度、被萃水相铜离子浓度、总氨浓度和pH值及相比、LIX84浓度对铜萃取率、共萃氨量的影响. 结果表明,随LIX84中TBP浓度升高,铜萃取率变化不大,负载有机相的共萃氨量明显降低. 有机相中TBP浓度为0.1 mol/L、LIX84浓度为40%、被萃水相铜离子浓度25 g/L、总氨浓度3 mol/L及pH值9.1、相比1:1、萃取时间30 min时,铜萃取率约为81%,与未添加TBP时基本一致,而负载有机相的共萃氨量由未添加TBP时的260 mg/L降至添加TBP后的85 mg/L.     

缓冲盐溶液反萃分离红霉素A、C的研究

用NaH2PO4-Na2HPO4缓冲盐溶液反萃醋酸丁酯相中的红霉素,以纯化酯相中的红霉素A。分别考察了缓冲盐pH值、相比(体积比)、温度对红霉素A、C反萃取的影响。实验结果表明:随着pH值的增加,红霉素A的反萃率大大减少,红霉素C的反萃率先增加后减小,当pH=8时,酯相中红霉素A纯度最高且损失最低;随着相比(A/O)的增加,红霉素A、C的反萃率及酯相中的红霉素A纯化效果都略有提高,但综合考虑反萃剂用量和红霉素A损失,可知相比(A/O)为2∶1时较优;随着温度的增加,红霉素A、C的反萃率都大大减小,且酯相中的红霉素A纯度略有下降,但因红霉素A反萃损失较少,可考虑在328 K时,反萃2次,除去大量红霉素C的同时损失较少的红霉素A。     

溶剂萃取动力学的研究 (Ⅰ)有机胺萃取红薯粉发酵清液中柠檬酸的速率

用上升液滴法研究了有机胺(简称 R_3N)萃取红薯粉发酵清液中柠檬酸(H_3A)的萃取速率,考察了有机相中添加剂(醋酸丁酯和油酸)对萃取速率的影响。结果表明苯取速率的经验方程式可表示为R=k_f[H_3A]_((B))~(0.5)[R_3N]_((0))[油酸]_((0)).     

双水相体系萃取天冬氨酸转氨酶

研究了不同的双水相体系对天冬氨酸转氨酶的萃取分离效果,对聚乙二醇/无机盐成相系统进行了系统的研究,初步确定PEG1000 Na2HPO4为研究体系,并考察体系pH值、无机盐对双水相体系分配系数和纯化系数的影响。当PEG1000的质量分数为18%、Na2HPO4的质量分数为20%时,双水相体系对天冬氨酸转氨酶的分离系数和纯化系数分别为2 36和2 94。     

Separation of five bioactive compounds from Glycyrrhiza uralensis Fisch using a general three-liquid-phase flotation followed by preparative high-performance liquid chromatography

ABSTRACT

Glycyrrhiza uralensis

Fisch is homologous medicine for food plant and health-protective affection in the human body system. To further understand the functions of G. uralensis Fisch, separation of the bioactive compounds from this natural product is very important. A general three-liquid-phase flotation (TLPF) technique was established to separate and concentrate five bioactive compounds from G. uralensis Fisch. The three-liquid-phase system, pH of initial aqueous phase, (NH₄)₂SO₄ concentration, nitrogen flow rate, and flotation time were investigated. The flotation efficiency of liquiritin apioside, liquiritin, and glycyrrhizic acid in the middle phase and semilicoisoflavone B and licoisoflavone B in the upper phase could reach 91.24%, 94.23%, 88.04%, 94.67%, and 96.44%, respectively. Furthermore, the established TLPF was used for separation of four kinds of anthraquinones from Cassiae Semen. The results showed that TLPF is feasible for separating the compounds with quite a different polarity from natural products.     

溶剂萃取1,2-环己二醇的研究

采用萃取平衡实验法,首次研究了用有机溶剂萃取水相中1,2-环己二醇的萃取热力学性质,为1,2-环己二醇的分离、提纯建立了一种新方法并提供了基础数据。考察了乙酸乙酯和乙酸丁酯作为萃取剂,苯、甲苯、环己烷、正庚烷、甲基丙基酮、1,2-二氯乙烷作为稀释剂时,对萃取水相中1,2-环己二醇的影响,并证实了该萃取过程为吸热过程。