Competitive transport of alkali metal ions from aqueous media into toluene solutions of 2-(sym-dibenzo-16-crown-5-oxy)-decanoic acid. A comparative study

Competitive permeation of alkali metal ions from an alkaline source phase into or through a toluene phase facilitated by the lipophilic crown ether carboxylic acid 2-(symdibenzo-16-crown-5-oxy)-decanoic acid is studied in liquid—liquid extraction, bulk liquid membrane transport, and emulsion liquid membrane transport. Most rapid transport was obtained in emulsion liquid membrane experiments. Some differences in selectivity orders for alkali metal permeation were observed for the three separation techniques.     

Studies on emulsion liquid membrane extraction of cephalexin

An experimental study on batch extraction of cephalexin using an emulsion liquid membrane system has been reported. The effects of surfactant, carrier and solute concentrations, phase volume ratio, stirring speed, and counterion concentration on the extraction rate were examined. Surfactant, carrier and diluent used were Span-80, Aliquat-336 and n-heptane–kerosene (1:1), respectively. Under the optimised experimental conditions, emulsion swelling was found to be marginal. By maintaining an appropriate pH gradient in the feed and receiving aqueous phase, facilitated transport could be realised. Selective separation of cephalexin from a mixture of 7-aminodeacetoxy cephalosporanic acid (7-ADCA) could be demonstrated in the emulsion liquid membrane system. A mathematical model based on mass transfer across aqueous boundary layer, interfacial chemical reaction and diffusion in the emulsion globule provides a reasonable fit of the experimental solute concentration versus time profiles in the emulsion liquid membrane system.     

环烷酸类载体液膜体系对金属离子传输机理的研究

本文先在大块液膜体系中以环已烷甲酸为载体,通过正交设计,系统地研究了各种因素对希土离子输送作用的影响规律。比较了相同条件下RE~(3+)(希土)同Na~+,NH_4~+、Ca~(2+)和Fe~(3+)等离子的输送作用。发现在适当条件下,无皂化的羧酸载体对RE~(3+)离子具有良好的输送效果,同时证实,羧酸输送RE~(3+)离子是通过三个H~+离子与一个RE~(3+)离子的交换,而当载体皂化时,皂化的载体直接与接收相H~+离子发生交换,从而降低了羧酸对RE~(3+)离子的输送和分离效果。 在大块液膜研究的基础上,建立了一个以无皂化的环烷酸为载体的乳状液膜体系,从模拟离子矿的硫酸铵浸出液中萃取希土,通过正交试验确定了最优的液膜萃取条件,希土萃取率达96％以上,富集度30～40倍。     

Application of an enzyme thermistor for the determination of glucose in complex fermentation media

An enzyme thermistor was used for on-line glucose determination during cultivation of Cephalosporium acremonium for a period of 160 h. The complex medium consisted of 100 g 1^?1 peanut meal. Automatic control and data registration were achieved by interfacing a process computer with the thermistor unit. Problem caused by long-term application are discussed. On-line and off-line data obtained with the enzyme thermistor are compared with the results obtained with a commercial glucose analyzer. The results of these experiments show that an enzyme thermistor can be used to determine glucose concentration in complex fermentation media under real cultivation conditions for about 60 h.     

Mathematical modeling of penicillin G extraction in an emulsion liquid membrane system containing only a surfactant in the membrane phase

An extraction experiment of penicillin G was performed in an emulsion liquid membrane system in which only ECA 4360J exists in the organic membrane phase without a predominant carrier, Amberlite LA-2, used in our previous works and it functions as a carrier as well as a surfactant. A permeation model for the present system has been developed as a primary study to examine the transport mechanism of penicillin G in the previous batch and continuous systems with two carriers of Amberlite LA-2 and ECA 4360J. The model takes into account the mass transfer in the external aqueous film, the extraction reaction between penicillin G and ECA 4360J at the external interface, the diffusion of penicillin G in the emulsion phase, the stripping reaction at the internal interface and the pH change of internal aqueous solution containing Na₂CO₃ with penicillin G transported into the internal phase. The experimental data were well fitted with the present model. Also, an expression for the reaction of penicillin G with ECA 4360J was obtained through a series of equilibrium measurements in liquid–liquid extraction system.     

Extraction of free phenols from blood by a liquid membrane enzyme reactor

The development of a liquid membrane enzyme reactor for the extraction of phenols from blood and plasma is described. Phenol permeation across the liquid membrane is studied, the transport of the toxins is linked with an enzymatic reaction. The encapsulation of the enzyme is described in detail. The stability of the multi-emulsion as well as the loss of enzyme activity during encapsulation and treatment axe examined thoroughly. The resulting liquid surfactant membrane emulsion is applied in in-vitro experiments to remove phenols from blood and plasma.     

Four-channel enzyme thermistor system for process monitoring and control in biotechnology

A newly developed four-channel enzyme thermistor system is presented and its application to biotechnological process monitoring is discussed. Different sugars were detected on-line during the cultivation of Cephalosporium acremonium and Bacillus licheniformis on technical media and during a starch hydrolysis process with immobilized thermostable enzymes. Immobilized enzymes and entrapped microorganisms were used as biological compounds in this biosensor.     

Liquid membrane transport: a survey

The literature pertaining to facilitated transport and liquid membrane separations is reviewed and summarized, especially work reported since 1977. Liquid membranes of all geometries are discussed, including immobilized liquid membranes and liquid surfactant or emulsion liquid membranes. Emphasis is placed on facilitated, or carrier-mediated transport in both configurations although other mechanisms such as coupled-transport and transport due to solubility differences are discussed. Mathematical modeling and analytical solutions for facilitated transport models are summarized. The possibility of industrial application of liquid membrane technology is mentioned and the most important experimental techniques for liquid membrane research are discussed. Also, directions for future research are recommended.     

利用原位水热合成在二氧化硅陶瓷管上制备高性能的Silicalite-1分子筛膜

 利用原位水热合成法在二氧化硅陶瓷管上成功制备出高性能的silicalite-1分子筛膜,并利用扫描电子显微镜进行了表征. 结果表明,在二氧化硅陶瓷管上合成的分子筛膜比在氧化铝陶瓷管上合成的分子筛膜具有更高的分离性能和热稳定性,说明二氧化硅载体更适合制备高性能的silicalite-1分子筛膜.     

Kinetic studies on the extraction of uranium(VI) from phosphoric acid medium by bulk liquid membrane containing di-2-ethylhexyl phosphoric acid

To go through the first stage of industrial solvent extraction process in order to recover uranium from phosphate rocks by liquid membrane techniques, as a simple model, the kinetics of facilitated transport of uranium(VI) from a dilute phosphoric acid medium into more concentrated phosphoric acid media as a receiving phase through a bulk liquid membrane containing di-2-ethylhexyl phosphoric acid as a carrier was studied. The influence of phosphoric acid concentration in the source and receiving phases, carrier concentration, type of solvent, stirring speed and temperature were investigated. The kinetic parameters (k _e, k _s, t _max, J _max) were calculated for the interface reactions assuming two consecutive, irreversible first-order reactions. The activation energy values were calculated as 29.40 and 19.51 kJ mol^?1 for extraction and stripping, respectively. The values of calculated activation energy indicated that both the extraction and stripping processes were controlled by mixed regime (both kinetic and diffusion). In addition, the influence of adding trioctyl-phosphine oxide into the membrane phase as a synergic agent on the transport kinetics was determined.     

β-Cyclodextrin derivative as chiral carrier in membrane transport of some aromatic amino acids

The chiral functionalized β-cyclodextrin (heptakis (2,3,6-tri-o-acetyl)-β-cyclodextrin) was studied as an extraction receptor in liquid–liquid extraction and carrier through bulk liquid membrane for highlighting its ability to enantiomeric discrimination of some native aromatic amino acids (tryptophane, phenylalanine, and tyrosine) and methylester derivatives (tryptophane methylester hydrochloride, phenylalanine methylester hydrochloride, and tyrosine methylester hydrochloride). The receptor exhibited carrier ability for aromatic amino acids transport through chloroform liquid membrane, especially for l-amino acids form aiming at their separation. Active transport of amino acids assisted by the pH gradient was carried out. Additional, the circular dichroism measurements were performed to point out the enantiomeric discrimination of aromatic amino acids by functionalized β-cyclodextrin. The results showed that the structural properties of amino acids are an important parameter in extraction and transport experiments.     

Thioether-mediated copper transport through liquid membranes with the aid of redox reaction

A thioether-mediated copper transport with the aid of redox reaction was studied in a polymer-supported liquid membrane and in a liquid surfactant membrane. A photochemical generation of the redox potential led to a photo-assisted copper separation and concentration system. Tetradentate thioethers 1 and 2 (L) selectively extracted copper ion into organic solution in the presence of a reducing agent, and served as a copper-selective carrier in a liquid membrane system. In the polymer-supported organic liquid membrane system, the thioether was dissolved in the membrane phase which separated the two aqueous solutions of different redox potentials. The copper ion was extracted into the membrane phase by formation of the [Cu^IL]⁺ ? X^? type complex on the reducing solution interface and permeated through the membrane toward the oxidizing solution interface, where the complex was decomposed to release the copper(II) species into the oxidizing aqueous solution. The nature of the system was studied in detail under various operational conditions (redox agents, pairing anion X^?, coexisting metals, etc.) and compared with that of the previously reported Bathocuproine-mediated system. The transport system was extended to the water-in-oil-in-water emulsion system (liquid surfactant membrane), and the selective concentration of copper ion from dilute external aqueous solutions into inner stripping solutions was achieved. Photo-induced redox reactions, triethanolamine—acriflavine—methyl viologen—hv and glucose—titanium oxide—hv, were successfully coupled to the systems, leading to a photo-assisted copper transport in the polymer-supported liquid membrane as well as in the liquid surfactant membrane. Tentative explanations were given on the nature of the membrane transport reactions.     

Ethanol removal from fermentation broth by gas membrane extraction

A new type of membrane extraction for in situ removal of ethanol from fermentation broth is presented. Aqueous solutions of propylene glycol are used as extractants. The extractatant and the broth are separated by a microporous hydrophobic membrane which is not penetrated by the broth or by the extractant. As a consequence a thin gas layer, essentially air, is immobilised within the membrane pores and separates the two liquid phases (i.e. a gas membrane). Vapour-liquid equilibria are established at both membrane sides; because glycols reduce the ethanol content of the equilibrium vapour phase with respect to the binary system, ethanol vapours preferentially diffuse through the stagnant gas layer.     

液膜分离富集、测定痕量钼

用乳状液膜体系对钼进行富集。该体系包括载体 ( 5,8-二乙基 - 7-羟基十二烷 - 6-单肟 ,简称LIX63)、表面活性剂 (N1 1 3C)、溶剂(煤油 )以及内相 ( 0 .1 5mol/LNaOH溶液 )。研究了乳状液膜的稳定性、温度、钼的浓度、外相的HNO3溶液浓度及乳水比等因素对分离富集钼的影响。实验表明 ,在适宜的条件下 ,钼的迁移率可达 99.5%～1 0 0 .2 %。该法已应用于富集、测定纯钨和钢铁中的痕量钼 ,结果相当满意     

Studies on transport mechanism of Cr(VI) extraction from an acidic solution using liquid surfactant membranes

A mathematical model for analysing the extraction of Cr(VI) from aqueous acidic solution by emulsion liquid membrane using Aliquat 336 as extractant and NaOH as stripping agent has been presented. The existing models developed so far do not account for the existence of different forms of Cr(VI) ions in the aqueous phase depending on pH conditions. Accordingly, in the present model, reaction equilibrium has been considered instead of distribution coefficient to represent realistically the transport mechanism for this type of system through liquid surfactant membrane. Unlike other models, liquid–liquid equilibrium of sodium hydroxide-chloride of Aliquat 336 has also been considered. The carrier thus exists in the membrane phase in hydroxide and chloride forms and extraction of hexavalent chromium from the external phase proceeds by the two carriers. The validity of the model has been checked from comparison of the simulated curves and experimental data using chemical reaction equilibrium constant and D_eff/R² as fitting parameters.     

Synchronized extraction and purification of L-lactic acid from fermentation broth by emulsion liquid membrane technique

This study aims to investigate the recovery of L-lactic acid from fermentation broth by an emulsion liquid membrane (ELM), made up of sunflower oil as the diluent, Sorbitan monooleate (Span 80) as the surfactant, Aliquat 336 as the carrier, and sodium hydroxide (NaOH) solution as the internal aqueous phase. Particularly, the ELM process was properly set up, through the identification of the optimal ELM operating parameters on the final extraction efficiency of L-lactic acid, including Span 80 concentration, NaOH concentration, Aliquat 336 concentration, stirring speed, phase ratio, and treatment ratio. The obtained results showed that the extraction efficiency of L-lactic acid reached up to 99% under the following optimal conditions: 10 minutes after contact time, 4% w/w Span 80, 3% w/w Aliquat 336, 0.1?N solution of NaOH, stirring speed of 300?rpm, phase ratio 1, and treatment ratio 0.25. A stable system without considerable emulsion swelling and breakage was monitored using a dynamic light scattering (DLS) apparatus for the selected optimal ELM operating parameters.     

Selective separation of aromatic hydrocarbons through supported liquid membranes based on ionic liquids

Ionic liquids are emerging as alternative solvents for volatile organic compounds traditionally used in liquid–liquid extraction and liquid membrane separation. In this paper, we examine whether room-temperature ionic liquids as a membrane solution can be utilized for hydrocarbon separation by using a supported liquid membrane. Aromatic hydrocarbons, benzene, toluene and p-xylene were successfully transported through the membrane based on the ionic liquids. Although the permeation rates through the membrane based on the ionic liquids were less than those of water, the selectivity of aromatic hydrocarbons was greatly improved. The maximum selectivity to heptane was obtained using benzene in the aromatic permeation and 1-n-butyl-3-methylimidazolium hexafluorophosphate in the liquid membrane phase.     

In Situ Biphasic Extractive Fermentation for Hexanoic Acid Production from Sucrose by Megasphaera elsdenii NCIMB 702410

Hexanoic acid production by a bacterium using sucrose as an economic carbon source was studied under conditions in which hexanoic acid was continuously extracted by liquid–liquid extraction. Megasphaera elsdenii NCIMB 702410, selected from five M. elsdenii strains, produced 4.69 g l^?1 hexanoic acid in a basal medium containing sucrose. Production increased to 8.19 g l^?1 when the medium was supplemented by 5 g l^?1 sodium butyrate. A biphasic liquid–liquid extraction system with 10 % (v/v) alamine 336 in oleyl alcohol as a solvent was evaluated in a continuous stirred-tank reactor held at pH 6. Over 90 % (w/w) of the hexanoic acid in a 0.5 M aqueous solution was transferred to the extraction solvent within 10 h. Cell growth was not significantly inhibited by direct contact of the fermentation broth with the extraction solvent. The system produced 28.42 g l^?1 of hexanoic acid from 54.85 g l^?1 of sucrose during 144 h of culture, and 26.52 and 1.90 g l^?1 of hexanoic acid was accumulated in the extraction solvent and the aqueous fermentation broth, respectively. The productivity and yield of hexanoic acid were 0.20 g l^?1 h^?1 and 0.50 g g^?1 sucrose, respectively.     

Mathematical modeling for facilitated transport of Ge(IV) through supported liquid membrane containing Alamine 336

A mathematical model was developed for the germanium-facilitated transport from a medium containing tartaric acid using Alamine 336 as a carrier. Modeling was carried out based on the extraction constant (K _ext) obtained from the liquid–liquid extraction (LLX) modeling. The LLX data were achieved from experiments with conditions being Alamine 336 concentrations of 0.1–10% v/v from a solution containing about 1.378 mmol/L Ge (100 mg/L) and tartaric acid as an anionic complexant. The LLX model was attained using the equilibrium-based procedure and fitted to extraction experimental data for various carrier concentrations. This model presented an accurate extraction constant (K _ext = 0.02) used in the facilitated transport modeling. The flat sheet supported liquid membrane (FSSLM) experiments were conducted in the condition of 1.378 mmol/L Ge (100 mg/L), tartaric acid concentration of 2.760 mmol/L, 1 M HCl as a stripping phase and various Alamine 336 concentrations in the range of 0–35% v/v. The FSSLM model was developed according to the Fick’s law, the diffusional transport, and equilibrium equations. According to the model, mass transfer and diffusion coefficients for various concentrations of the carrier were found. In addition, the calculated and experimental values had a good correlation with together showing the validity of the model. This model can be used in the further process simulation such as hollow fiber SLMs.     

Carrier-mediated transport of actinides and rare earth elements through liquid and plasticized membranes

The first works in this field were realized approximately 25 years ago, when BLOCK et al. reported^1,2 their studies about carrier-mediated transport (also called pertraction or membrane extraction) of uranium through plasticized membranes with neutral esters derived from phosphoric acid. At this time, the methodical principles of selective pertraction of ionic compounds through so-called bulk liquid membranes containing carriers were known.³ However, these membranes, similarly as plasticized membranes, have not achieved a broader use. This is probably because bulk liquid membranes are from a technical point of view fairly distant from the idea of a typical membrane system, and plasticized membranes (sometimes also called gel membranes) present great resistance. By the end of the 1960's and at the beginning of the 1970's, LI^4–7 and CUSSLER⁸ worked out the principles for two widely used pertraction techniques, called pertraction through emulsion liquid and supported liquid membranes (ELM and SLM). These two techniques not only have greatest significance in laboratory practice, but they also are interesting for technological aims because of the attainable large phase boundaries, e. g. 10³–10⁴ m²/m³. Many ways to arrange membrane systems are described in papers.^9,10 Recently, the significance of carrier-mediated transport through liquid membranes has grown to have (since 1980) separate section at the International Solvent Extraction Conference.This paper does not deal with mathematical models and the mechanism of pertraction in general, but it gives an overview of results obtained in publications referring to pertraction of two related element groups — actinoids and rare earth elements — using various membrane types.