Mixed Surfactant-Based Reverse Micellar Extraction Studies of Bovine Lactoperoxidase

The suitability of reverse micellar extraction for recovery of bovine lactoperoxidase (LP) from aqueous solution was evaluated using systems formed by ionic and nonionic surfactant mixtures. The influence of ionic surfactant concentration, organic solvent, and pH on the extraction of LP into the reverse micellar phase was studied. The Tween® series surfactants with Aerosol-OT (bis-(2-ethylhexyl) sulfosuccinate) showed better extraction of LP in the reverse micelles (RM) compared to the Triton® and Span® series of surfactants. Complete extraction of LP from an aqueous phase of initial concentration 25 mg L⁻¹ occurred with the RM formed by 90 mM Aerosol-OT/8 mM Tween® 80 in isooctane. The optimal pH, ionic strength, and positively charged ionic surfactant concentration for back extraction were also studied and a maximum of 95.5% back extraction efficiency and 66% LP activity recovery was obtained for a pH of 10.5,1 M KCl and 60 mM cetyltrimethylammonium bromide system.     

Carl Hanson Medal

ABSTRACT

Nondispersive equilibrium separation of citric acid from an aqueous solution by reversible chemical complexatlon with trioctyl amine in a diluent of methyl isobutyl ketone is achieved in a microporous hydrophobic hollow fiber extractor. The extractor had a shell-and-tube configuration : a total of 102 hydrophobic polypropylene (Celgard X-20, 240 μm id, 290 μm od, Hoechst Celanese) hollow fibers potted in epoxy in a stainless steel tube of 0.46 cm id. The effective fiber length vas 18.5 cm and surface area/volume was 46.8 cm. Theoretical models have been developed to predict the rate of extraction of citric acid in such systems. It essentially considers diffusion of solute molecules through the boundary layers of the two phases, in addition to the diffusion through the organic liquid occupying the membrane pores, and reversible chemical equilibrium at the phase interface. Conventionally in an aqueous-organic system having a high distribution coefficient for small solutes with a hydrophobic fiber and organic in pores, the aqueous boundary layer resistance controls. Here that is true also except when the membrane resistance of the large citric acid-amine complex diffusing through the organic-filled pores is higher than the aqueous phase boundary layer resistance. Experimental observations show further that the back extraction rate of citric acid present in the solvent (amine-organic diluent) into aqueous sodium hydroxide is much lover than the extraction rate for such a system in the sane hollow fiber extractor.     

中空纤维膜萃取镉离子的研究

处理重金属离子水溶液是环境治理中的一个重要方面 ,应用新型膜萃取技术对去除水溶液中镉离子进行了研究。首先测定镉离子在不同萃取体系中的分配系数 ,选择合适的萃取剂 ,在中空纤维膜器中研究膜萃取去除镉离子的分离效果和传质特性 ,探讨不同装填因子、两相流速、水相初始浓度等实验条件对分离和传质的影响。实验结果表明 ,体积分数为 5 0 %的P2 0 4 正庚烷溶剂对于镉离子有较好的萃取效果。当装填因子为 0 .732 8时 ,经 33cm长的中空纤维膜器一级萃取可将溶液质量浓度由 40 0mg/L降至 0 .2mg/L以下 ,证明了膜萃取的高效性     

Modeling and simulation of mass transfer in near-critical extraction using a hollow fiber membrane contactor

In this study is presented a general methodology to predict the performance of a continuous near-critical fluid extraction process to remove compounds from aqueous solutions using a hollow fiber membrane contactor. The stabilization of the gas-liquid interface in the membrane porosity and a high surface area to contact both phases represent some of the advantages that hollow fiber contactors offer over conventional contactor devices for the extraction of compounds from liquid feeds.A mathematical model has been developed integrating a resistances-in-series mass transfer system that takes into account boundary layers, membrane porosity and thermodynamic considerations with mass balances of the membrane contactor. Simulation algorithms were easily implemented with low calculation requirements.The system studied in this work is a membrane based extractor of ethanol and acetone from aqueous solutions using near-critical CO₂. Predictions of extraction percentages obtained by simulations have been compared to the experimental values reported by Bothun et al. [2003a. Compressed solvents for the extraction of fermentation products within a hollow fiber membrane contactor. Journal of Supercritical Fluids 25, 119-134]. Simulations of extraction percentage of ethanol and acetone show an average difference of 36.3% and 6.75% with the experimental data, respectively. More accurate predictions of the extraction of acetone could be explained by a better estimation of the transport properties in the aqueous phase that controls the extraction of this solute.When the model was validated, the effect of the configuration and the operating parameters was studied and local mass transfer resistances were evaluated. The proposed approach allows the evaluation of the relevance of membrane hydrophobicity for extraction in solutions under different thermodynamic conditions. This original methodology based on well-known phenomenological equations represents a general approach which could be applied in other processes using membrane contactors with different configurations.     

苯酚在浊点萃取中凝聚层相的增溶规律

采用分光光度法测定了苯酚在非离子表面活性剂单相胶束溶液中和在非离子表面活性剂两相浊点萃取时凝聚层相中的增溶结果.实验表明：溶质在凝聚层相的增溶与表面活性剂形成胶束的结构有关.当凝聚层相的表面活性剂形成正相胶束时,溶质在凝聚层相的增溶规律和在表面活性剂胶束溶液中的增溶规律一致;当凝聚层相的表面活性剂形成反相胶束时,溶质在凝聚层相和在溶液相的浓度关系可理解为在这两种溶剂之间的分配随着凝聚层相的含水率逐渐降低趋近于一定值,溶质的分配系数也趋近于一定值.     

Prediction of Equilibrium Partitioning of Nonpolar Organic Solutes in Water‐ Surfactant Systems by UNIFAC and COSMO‐RS Models

In the present study the potential of two thermodynamic‐based models (the group‐contribution UNIFAC model and the a priori predictive COSMO‐RS model) to predict solute partitioning in aqueous surfactant solutions is evaluated. In order to take into account the small size of micelles, the UNIFAC model was extended by the interfacial contribution based on the Gibbs‐Thompson equation. The applicability of the approach was successfully proved for the partitioning of nonpolar solutes (toluene, p‐xylene) in aqueous solutions of nonionic surfactants. The original COSMO‐RS model underestimates the concentration of the solute in the aqueous phase in the case of micellar systems since it does not account for the small size of micelles. At the same time, this model gives quantitative results for the octanol/water partition coefficients of both solutes under study leading to the conclusion that the affinity of both solutes to a certain solvent is well described. Thus, extending the COSMO‐RS by the interfacial term seems to be promising.     

Amino acid solubilization in cationic reversed micelles: factors affecting amino acid and water transfer

The aim of this work is to investigate the driving forces involved in amino acid solubilization in cationic reversed micelles, and to determine in which way different parameters affect the reversed micellar structure and amino acid solubilization, in order to select the best conditions to optimize amino acid extraction. To this end, extraction equilibrium experiments were performed using different experimental conditions and three amino acids with different structures: aspartic acid – a hydrophilic amino acid, phenylalanine – a slightly hydrophobic amino acid, and tryptophan – a hydrophobic amino acid. The study of the effect of amino acid related parameters, such as pH and the initial amino acid concentration in the aqueous phase, and the effect of parameters that influence the reversed micellar structure, such as surfactant concentration, ionic strength and co‐surfactant concentration, provides useful information about the driving forces involved, solute–micelle interfacial interactions and solute location in the cationic system trioctylmethylammonium chloride (TOMAC)/hexanol/n‐heptane. These parameters can be adjusted to optimize amino acid extraction. It is shown that amino acids with the same isoelectric point can be selectively separated by exploring the different interactions they establish with the reversed micellar interface. © 1999 Society of Chemical Industry     

Recovery of Copper Ions from Wastewater by Hollow Fiber Supported Emulsion Liquid Membrane

Recovery of copper ions from wastewater using a hollow fiber supported emulsion liquid membrane (HFSELM) was studied with LIX984N as carrier, kerosene as diluents, and sulfuric acid solution as strippi...     

Extraction Kinetics of Rare Earth Metals with 2-Ethylhexyl Phosphonic Acid Mono-2-ethylhexyl Ester Using a Hollow Fiber Membrane Extractor

Abstract

A kinetic study concerning chemical complexation-based solvent extraction of rare earth metals with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester dissolved as an extractant in n-heptane was carried out using a microporous hydrophobic hollow fiber membrane extractor. The effects of concentration of chemical species in aqueous and organic feed solutions on the apparent permeabilities of metal species for extraction and stripping, respectively, were investigated to clarify the permeation mechanism. From the experimental results it was predicted that the permeation rate is controlled by diffusion of the chemical species in aqueous and organic phases and by interfacial chemical reaction. The experimental data were analyzed by the diffusion model accompanied with an interfacial reaction, taking into account the velocity distributions of the aqueous and organic phases through the inner and outer sides of the hollow fiber.     

Hydraulics and Mass Transfer Efficiency of a Commercial-Scale Membrane Extractor

Abstract

In recent years there has been significant interest in utilizing microporous hollow fiber membranes for liquid-liquid extraction. The membrane extractor resembles the shell and tube heat exchanger with the tube section composed of 1000–2500 fibers/in². The diameter of each fiber is approximately 300 microns. In this process, the feed may be passed through the shell side, while the solvent is passed through the fiber side, or vice versa. Mass transfer occurs across the liquid-liquid interface formed in the pores of the fiber wall. The advantages of this technology are high throughput capacities, independence of density difference between the feed and solvent, and potentially high mass transfer areas. The mass transfer performance of an available commercial scale nonbaffled membrane extraction module was determined to be lower than expected from results obtained in smaller scale modules. Mass transfer studies of a commercial-scale membrane extraction module at the Separations Research Program have shown that a significant portion of the fibers are bypassed by the shell side fluid and consequently only a fraction of the total fiber surface area is utilized. A hydraulic study using a dye tracer technique verified this finding with an aqueous flow on the shell side. A model which incorporates mass transfer correlations reported by others has been developed and shown to have excellent agreement with the experimental data obtained. In this paper, the efficiency of the membrane extractor is compared with conventional spray, sieve tray, and packed columns; the effect of shell side bypassing is also presented.     

Preparation of a heterogeneous hollow‐fiber affinity membrane modified with a mercapto chelating resin

A high‐quality, heterogeneous hollow‐fiber affinity membranes modified with mercapto was prepared through phase separation with blends of a chelating resin and polysulfone as membrane materials, poly(ethylene glycol) as an additive, N,N‐dimethylacetamide as a solvent, and water as an extraction solvent. The effects of the blending ratio and chelating resin grain size on the structure of the hollow‐fiber affinity membrane were studied. The effects of the composition of the spin‐cast solution and process parameters of dry–wet spinning on the structure of the heterogeneous hollow‐fiber affinity membrane were investigated. The pore size, porosity, and water flux of the hollow‐fiber affinity membrane all decreased with an increase in the additive content, bore liquid, and dry‐spinning distance. With an increase in the extrusion volume outflow, the external diameter, wall thickness, and porosity of the hollow‐fiber affinity membrane all increased, but the pore size and water flux of the hollow‐fiber affinity membrane decreased. It was also found that the effects of the internal coagulant composition and external coagulant composition on the structure of the heterogeneous hollow‐fiber affinity membrane were different. The experimental results showed that thermal drawing could increase the mechanical properties of the heterogeneous hollow‐fiber affinity membrane and decrease the pore size, porosity, and water flux of the heterogeneous hollow‐fiber affinity membrane, and the thermal treatment could increase the homogeneity and stability of the structure of the heterogeneous hollow‐fiber affinity membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Modeling and Experimental Data for the Reverse Micellar Extraction of Proteins Using a New Surfactant

ABSTRACT

In this study the reverse micellar extraction of α-chymotrypsin using bis(2,4,4-trimethylpentyl) sodium dithiophosphinate as the surfactant has been investigated. Experiments were performed to determine the effects of pH and salt concentration on the reverse micellar extraction and backward extraction of α-chymotrypsin in isooctane/decanol mixtures. The results showed that both pH and salt concentration influence the reverse micellar extraction of α-chymotrypsin. The pH affects the extraction of the protein through changing the sign and number of the charges carried by protein molecules and thereby affects their interactions with the charged head groups of the surfactant molecules. It was found that at high pH values the hydrogen ions compete with positively charged protein molecules and exchange with the counterions of the surfactant molecules, and as a result destroy the reverse micelles. This effect was exploited for the backward extraction of protein molecules from the reverse micellar phase. A model has been developed to correlate the experimental data of reverse micellar extraction of proteins. In the model the reverse micelles were treated as noninteractive ion-exchange sites. The activity coefficient of the protein molecules in reverse micelles was represented by the model proposed by Pitzer. It has been shown that the model can correlate the experimental data obtained in this work and those reported in other studies.     

Reverse Micellar Extraction of Bromelain from Pineapple (Ananas comosus L. Merryl) Waste: Scale-up,Reverse Micelles Characterization and Mass Transfer Studies

Scale-up studies for phase transfer mode of reverse micellar extraction are attempted for the separation and primary purification of bromelain (EC 3.4.22.33) from pineapple (Ananas comosus L. Merryl) waste. Characterization of reverse micelles and mass transfer studies for the real system has been attempted for the first time. Scale-up of the extraction process employing commercial grade surfactant cetyltrimethylammonium bromide (CTAB) and solvent isooctane resulted in purification of 2.43 fold with an activity recovery 81.3%. The reverse micellar size estimated using empirical and geometrical models indicated that the reverse micelles are large enough (R_m = 7.2–9.6 nm) to host bromelain molecules that are relatively smaller in size (～1.67 nm). The studies on the kinetics of mass transfer indicated a relatively slower rate (by ～34%) of mass transfer in case of back extraction compared to forward extraction. Process scale-up did not significantly affect the extraction efficiency whereas purity of phase components played a major role. The mass transfer across the phases was high in the initial period of mixing for both forward and back extractions.     

Forward and Backward Extraction of Methylene Blue by using AOT/Isooctane Reversed Micellar Solution

Organic dyes, which are contained in industrial effluents, should be removed to avoid health hazards and destruction of the ecosystem. In this study, the extraction of methylene blue from aqueous solution into AOT/isooctane reversed micellar solution was investigated. It was found that methylene blue was solubilized into the waterpool within reversed micelles by electrostatic interaction with AOT. The extraction ratio of methylene blue increased with an increase in AOT concentration and a decrease in salt concentration. The methylene blue extracted reversed micelles could be recovered into fresh salt solution with high concentration. It is considered that the main driving force of forward and backward extraction of methylene blue is electrostatic interaction between cationic dye, methylene blue, and anionic surfactant, AOT. The deterioration of the forward and backward extraction behavior by using AOT/isooctane reversed micellar solution reused was not observed.     

双水相胶束萃取苯酚

根据胶束的加溶原理和非离子表面活性剂系统在浊点温度以上自动分相的现象 ,采用TritonX - 10 0胶束系统萃取苯酚 .结果表明 :苯酚的比胶束加溶量与其在水相的平衡浓度成比例关系 .测定了比例系数 ,即加溶平衡常数 .由此建立了数学模型 ,讨论了表面活性剂浓度、溶质浓度、pH值等因素对萃取率的影响 .模型计算结果和实验结果都说明 ,调节pH值可以反萃取苯酚的原因是苯酚电离改变了加溶平衡常数     

Recovering phenanthrene from spiked sand by a combined remediation process of micellar solubilization and cloud-point extraction

A remediation process, which combines the micellar solubilization and the cloud-point extraction technique by a nonionic surfactant Tergitol 15-S-7, was used to decontaminate phenanthrene, as a model hydrophobic pollutant, from spiked sand samples. A first-order kinetics model was employed to describe the solubilization behavior of phenanthrene well. It was observed that presence of surfactant decreased the mass-transfer coefficient of phenanthrene from sand surface to surfactant solutions, however, higher solubilization rate was obtained due to enhanced aqueous solubility and, thus, the larger driving force resulted from solublization. Cloud-point extraction was used to concentrate the phenanthrene solubilized in the washing solutions in an attempt to minimize the amount of wastewater. The extraction was carried out, subsequently, at room temperature by adding sodium sulfate to suppress the cloud-point low enough to induce phase-separation of the surfactant-rich phase with a minimal phase volume from the coexisting water phase. Recoveries higher than 93% were achieved in the combined process of micellar solubilization and cloud-point extraction on ultimate removal of immobilized phenanthrene sorbed on sands. The results showed that this combined process is efficient in recovering phenanthrene sorbed and immobilized on sands from contaminated sites, and produces only minimal amount of wastewater, i.e. less than 3% of its original volume.     

CFD simulation of acetone separation from an aqueous solution using supercritical fluid in a hollow-fiber membrane contactor

In the present study, separation and mass transfer of acetone using a polymeric hollow fiber membrane by a supercritical fluid as a dense solvent was simulated. The propane is used as supercritical fluid for extraction of acetone. The simulated hollow-fiber membrane contactor has three compartments: tube, porous membrane and shell. The aqueous solution and solvent pass in the lumen and shell sides, respectively. The model equations have been solved by CFD technique using a finite element as numerical method. The simulation results were compared with experimental data obtained from literature and showed great agreement with the measured values. The simulation results of acetone extraction also showed that reducing the feed rate and increasing the solvent velocity will enhance the separation of acetone.     

Activity of horseradish peroxidase in aqueous and reverse micelles and back‐extraction from reverse‐micellar phases

Studies on the activity of the enzyme horseradish peroxidase (HRP) have been carried out in micellar as well as reverse‐micellar media. The activity of the enzyme was studied in the presence of different classes of surfactants – ionic as well as non‐ionic. In aqueous media, the activity of the enzyme varied depending on whether the concentration of the surfactant used was above or below the critical micellar concentration (CMC). The enzyme was also studied in reverse‐micellar systems. HRP was introduced into the reverse micellar phase by the injection method and its activity within the reverse micelles was determined. The effect of water to surfactant ratio (W_o) on activity within reverse micelles was studied, and an almost two‐fold increase in activity was seen when the enzyme was encapsulated within reverse micelles of aqueous phase fractional hold‐up (?) of 0.0072 (v/v) consisting of sodium bis‐(2‐ethylhexyl) sulfosuccinate (AOT) in isooctane at a W_o of 20. The activity of HRP was measured over a wide range of AOT concentrations having different W_o values. Back‐extraction of HRP from these reverse micelles was carried out at varying ionic strengths of phosphate buffer. Back extraction was found to be highest at pH 7.0 in 40 mol m^?3 phosphate buffer and 100 mol m^?3 sodium chloride. © 2001 Society of Chemical Industry     

Computational Simulation of Mass Transfer in Molecular Separation Using Microporous Polymeric Membranes

Computational simulation was conducted to predict mass‐transfer phenomenon in the molecular separation of solute using microporous membrane contactors. Both diffusional and convectional mass‐transfer mechanisms were considered. The membrane system was a hollow‐fiber contactor in which an aqueous phase containing an organic compound was contacted with an organic phase for extractive separation of the solute. Benzoic acid was used as the solute. The main focus was on understanding the mass transfer of solute in the process. The concentration equation for the solute was solved numerically using a computational fluid dynamics approach. It was found that the model can predict the solute transport from the aqueous phase to the organic phase and can be used as a predictive model for process understanding.     

膜萃取防止溶剂污染的优势

本文以３％ＴＢＰ／苯酚／水为实验体系在不同的膜器中对膜萃取过程中料液对萃取剂的夹带,即溶剂的二次污染进行了研究。在保持膜两侧压降不变的情况下对进口和出口处料液的ＣＯＤ值进行了测定,并与传统的溶剂萃取方法相比较。结果表明,膜萃取中料液中溶剂只有少量的夹带,并且夹带量与操作条件和膜构件基本无关。