Permeability through cellulose membranes grafted with vinyl monomers in a homogeneous system. VIII. N-vinylpyrrolidone-grafted cellulose membranes

The homogeneous grafting of N-vinylpyrrolidone (NVP) onto cellulose was carried out in a dimethyl sulfoxide/paraformaldehyde (DMSO/PF) solvent system. The diffusive permeabilities of solutes through the NVP-grafted cellulose membranes, apparent activation energy for solute permeation through them, states of water in them, and their microphaseseparated structures were investigated. The solute permeability through the grafted membranes was superior to that through the cellulose membrane cast from the DMSO/PF solution of cellulose. The total water and nonfreezing water contents of the grafted membranes were larger than those of the cellulose membrane. The difference in permeability through the membranes was not correlated quantitatively with the amount of each state of water in them. Activation energies for permeation of solutes through the grafted membranes were similar to those through the cellulose membrane. © 1994 John Wiley & Sons, Inc.     

反渗透过程溶质脱除率方程

<正>溶解扩散理论、摩擦模型和表面力-孔流模型假设稳态时膜中溶质通量恒定“-”。本文分 析了该假设存在的理论依据,并基于膜的吸附-扩散模型’‘’建立了反渗透过程溶质脱除率方 程。     

LIQUID MEMBRANE TRANSPORT OF CEPHALOSPORIN ANTIBIOTICS: EFFECT OF SOLUTE CHEMICAL NATURE ON CARRIER SPECIFICITY

Cephalosporin antibiotics were transported from a dilute aqueous solution (feed phase) through a bulk liquid membrane containing Aliquat-336 as an anion exchange carrier in n-butyl acetate as the solvent to another aqueous solution (receiving phase) of lower pH. Under appreciable pH gradient of the feed and receiving phases, facilitated uphill transport could be obtained. Under the optimal pH condition, the intial solute flux across the bulk liquid membrane could be correlated well with the hydrophobicity of the solutes. A linear correlation exists between the initial solute flux and hydrophobicity, indicating that the solute of higher hydrophobic nature are transported at a higher rate in the bulk liquid membrane involving the specific carrier. The correlation appears to be derived from a linear dependenc of solute hydrophobicity on equilibrium constant of the reactive extraction system being exploited in the bulk liquid membrane.     

反渗透、纳滤过程的物理化学研究(Ⅰ)多孔膜的溶质脱除率方程和膜渗透通量方程

引言 溶解扩散模型、摩擦模型、Sourirajan方程和表面力孔流模型均假设稳态条件下溶质通量和溶液体积通量恒定[13].     

乳化液膜萃取乳酸稀溶液过程中的渗透溶胀及模拟

根据膜相中载体萃取的机理,指出载体在萃取溶质后形成的络合物具有一定的亲水性．采用气相色谱法,分别对含有表面活性剂和载体的膜相在与乳酸溶液接触后的溶水率进行了测定,结果发现其溶水率远高于与无溶质的外相水接触后的膜相溶水率．所以渗透溶胀进人内相的水除表面活性剂分子结合的迁移外还有载体-溶质络合物结合水．从而提出了实际萃取过程中乳化液膜渗透溶胀的反应-溶解-扩散机理,并提出了相应的数学模型,经与实验数据比较,结果吻合较好．     

Studies on syntheses and permeabilities of special polymer membranes: 33. Permeation behaviour of aqueous alcohol solution through cellulose membranes

The permeabilities of various aqueous alcohol solutions through cellulose membranes were investigated by changing the preparation conditions of membranes, the feed concentration, and the feed solute, etc. The permeation rates for aqueous solutions of alcohols, glycols, glycerol, trihydroxyl benzene were greater than for pure water. This permeation phenomenon could be explained by some permeation models considering water cluster, activation of water molecules (second bound water-like) attached weakly to the bound water in cellulose membrane, and the surface of cellulose membrane, and plasticization of cellulose molecules.     

纤维素直接溶解成膜及其分离特性研究进展

借鉴纺织行业Lyocell纤维制备过程中采用的溶解方法,以N-甲基吗啉-N-氧化物（NMMO）为溶剂物理溶解纤维素,制备出了新型纤维素膜,并对其性能进行了测试.结果表明通过溶剂法制备的新型纤维素膜,应用潜力主要表现在3个方面：在湿态条件下对酸性气体具有较好的渗透性能;经过改性加入亚砜基团的纤维素膜对SO₂表现出较高且稳定的渗透性;因为纤维素的强亲水性,该膜应用于油水分离,其耐污染能力较强.     

Studies on syntheses and permeabilities of special polymer membranes. X. Effects of conditions of membrane preparation on permeation characteristics of cellulose acetate membranes in separation of aqueous polymer solutions

The effects of casting solvents, dissolution temperature of casting solution, and pH and temperature of gelation solution, etc. on the permeation characteristics of cellulose acetate membranes in the separation of polymers from their aqueous solutions were investigated, using aqueous solutions of poly(ethylene glycol) and poly(vinyl alcohol) as feed. The permeation characteristics were influenced significantly by the conditions of membrane preparation and of the permeation. It was found that a concentration polarization at the membrane surface occurred with poly(vinyl alcohol) molecules, but it was very small with poly(ethylene glycol). The above results were discussed in detail from points of view of structure of the resulting membranes and the interactions between the solvent, the solute in the feed and the cellulose acetate molecules.     

预分散溶剂萃取分离苯酚溶液的研究

Predispersed solvent extraction (PDSE) is a new method for separating solutes from aqueous solution by solvent extraction and one which has shown promise for extraction from extremely dilute solution very efficient and very quick. The use of colloidal liquid aphrons in predispersed solvent extraction may ameliorate the problems such as emulsion formation, reduction of interracial mass transfer and low interfacial mass transfer areas in solvent extraction process. In present paper, colloidal liquid aphrons are successfully generated using kerosene as a solvent,tributyl phosphate(TBP) as an extractant, sodium dodecyl benzene sulphate(SDBS) as surfactant in aqueous phase and Tween-80 in oil phase. Extraction of phenol from dilute solution was studied by using colloidal liquid aphrons and colloidal gas aphrons in a semi-batch extraction column. It has been found that the PDSE process is more suitable for extraction of dilute solutions. It has also been discovered that the PDSE process has a great advantage over traditional single-stage extraction process.     

Extraction of 4‐Hydroxycinnamic Acid from Aqueous Solution by Emulsion Liquid Membranes

Abstract

This work reports a study of 4‐hydroxycinnamic acid extraction by emulsion liquid membranes. The effect of the presence of additives in the membrane phase on solute permeation was tested. The membrane with 2 wt.% of isodecanol, 2 wt.% of ECA4360J, and Shellsol T as diluent was selected to examine the permeation of 4‐hydroxycinnamic acid. The modeling of solute extraction was done by taking into account the mass transfer in the external phase and globule, and the reaction between the diffusing component and the stripping reagent. The agreement between the calculated results and the experimental data was found satisfactory.     

Studies on syntheses and permeabilities of special polymer membranes. V. Effect of casting solution composition on permeation characteristics of cellulose acetate membranes in separation of aqueous polymer solutions

The permeation characteristics of cellulose acetate membranes in separation of polymers from their aqueous solutions were investigated by changing the preparation conditions of the membranes, that are the solvent evaporation period and the casting solution composition consisting of a mixture of cellulose acetate (CA), acetone (A), and formamide (FA). The rates of pure water permeability were influenced remarkably by the solvent evaporation period and the casting solution composition. When the solvent evaporation period was short, the rates of pure water permeability increased with a decrease in A/CA, increase in FA/A, and increase in FA/CA in the casting solution. From the experimental results using poly(vinyl alcohol) as poly(ethylene glycol) as feed solute, it was seen that the changes of solvent evaporation period and casting solution composition related to the change of microporous structure of the resulting membranes. The effect of feed concentration and operating pressure on the permeation characteristics were also studied. There was found a concentration polarization of poly(vinyl alcohol) molecules on the surface of the membrane, and a compaction of the membrane occurred under pressure.     

Extraction of a dissolved organic contaminant from water into an aqueous surfactant solution across a microporous membrane

A novel extraction process, aqueous micellar solvent extraction (AMSE), was demonstrated. In ASME an solute is extracted from a wastewater across a microporous membrane into an aqueous surfactant solution containing micelles that solubilize the solute. The membrane retains the surfactant micelles in the aqueous micellar solvent. ASME was carried out in hollow fiber ultrafiltration modules with benzoic acid as the solute and a fatty amine ethoxylate surfactant. Flowing the micellar solvent through the fibers and the wastewater outside gave good extraction and low contamination of the treated water by surfactant. The major resistance to extraction of solute was diffusion across the wall of the hollow fiber.     

预分散溶剂萃取平衡与传质特性

预分散溶剂萃取(predispersed solvent extraction,简称PDSE）是一种新型的液-液萃取方法.该过程首先将溶剂制成胶质液体泡沫(colloidal liquid aphron ,简称CLA),同时借助胶质气体泡沫(colloidal gas aphron,简称CGA)实现溶质的分离.本文以磷酸三丁酯（TBP）-煤油为溶剂,以十二烷基苯磺酸钠（SDBS）为水相表面活性剂,以TWEEN 80为油相表面活性剂制备了胶质液体泡沫（CLA）. 用十六烷基三甲基溴化胺（HTAB）为水相表面活性剂制备了胶质气体泡沫（CGA）. 利用半间歇式PDSE过程萃取苯酚溶液.研究了pH值、表面活性剂浓度、相比等对萃取率和平衡分配系数的影响.实验发现,PDSE过程更适用于小相比（油相∶水相为1∶1000或更小）和极稀溶液的萃取.实验还发现, PDSE过程的萃取率随着CLA中TBP浓度的增加而增加, 随相比的增加而提高.利用刚性球模型计算了CLA的传质系数,并与传统的液滴进行了比较.在相同的粒径下,CLA比传统的液滴具有更高的分散相总传质系数;与传统萃取塔中存在的液滴相比,CLA也具有一定的优势.此外,对于两者K_da的比较,更体现了CLA的优越性.     

Mass transfer enhancement in supercritical fluid extraction by acoustic waves

A computational fluid dynamics model of extraction of a solute (caffeine) from a porous solid matrix (coffee beans) using a supercritical solvent (carbon dioxide) is developed. Supercritical fluid extraction of a solute from a solid matrix is a slow process even when solute free solvent is circulated. The use of acoustic waves represents a potential efficient way of enhancing mass transfer processes. The effect of acoustically excited flows on supercritical fluid extraction from a porous solid matrix is investigated. The mathematical model considers diffusion-controlled regime in the porous solid matrix and convective-diffusive transport in the bulk fluid. Henry's law is used to describe the equilibrium states of the solid and the fluid phases. Accurate representation of the thermo-physical properties of supercritical solvent is considered by using the NIST Standard Reference Database 12. The conservation equations for mass, momentum, energy and species are numerically solved using implicit finite volume method. The effect of process parameters, such as initial state (pressure and temperature) of solvent and acoustic waves on the yield of solute extraction is also investigated numerically.     

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.     

Use of Liquid Chromatography for Studying Reverse Osmosis and Ultrafiltration

Abstract

A method of observing the preferential adsorption of solute or solvent onto a polymer surface by liquid chromatography is illustrated, and the results are discussed in relation to the solute separation by reverse osmosis and membrane fouling. This method shows the existence of a preferentially adsorbed water layer at the polymer-solution interface, where its amount and thickness depend on the polymer material. The adsorption data of undissociated organic solutes indicate that cellulosic materials are intrinsically less susceptible to fouling by such solutes than synthetic polymer materials. It is also shown that the steric repulsion involved in the solute's distribution between the interfacial water phase and the bulk water phase is not sufficient to describe the solute transport through the membrane, and an additional steric effect associated with the frictional force working on the solute molecule in the membrane pore has to be considered.     

Gas permeation performance of cellulose hollow fiber membranes made from the cellulose/N‐methylmorpholine‐N‐oxide/H2O system

Cellulose hollow fiber membranes (CHFM) were prepared using a spinning solution containing N‐methylmorpholine‐N‐oxide as solvent and water as a nonsolvent additive. Water was also used as both the internal and external coagulant. It was demonstrated that the phase separation mechanism of this system was delayed demixing. The CHFM was revealed to be homogeneously dense structure after desiccation. The gas permeation properties of CO₂, N₂, CH₄, and H₂ through CHFM were investigated as a function of membrane water content and operation pressure. The water content of CHFM had crucial influence on gas permeation performance, and the permeation rates of all gases increased sharply with the increase of membrane water content. The permeation rate of CO₂ increased with the increase of operation pressure, which has no significant effect on N₂, H₂, and CH₄. At the end of this article a detailed comparison of gas permeation performance and mechanism between the CHFM and cellulose acetate flat membrane was given. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1873–1880, 2004     

Studies of Ion Transport through a Liquid Membrane by Using Crown Ethers

Abstract

Studies on ion transport through a liquid membrane system composed of two extraction processes have been carried out. Kinetic models based on extraction processes with consideration of the controlled parameters were developed for mediated ion transport through liquid membranes, especially those using crown ethers as the ion carrier. A study of the concentration change in the receiving or source phase envisages the determination of the equilibrium constant by a kinetic method corresponding to the chemical reaction at the interface as well as the maximum initial flux through the membrane. The equilibrium constant values determined by the kinetic process were checked by the solvent extraction method.     

正渗透过程中汲取质反向渗透研究进展

正渗透(FO)作为一种浓度驱动的膜技术,因其膜污染轻、能耗低和回收率高等优点而逐渐成为膜技术领域的研究热点之一。汲取质的反向渗透是正渗透过程中不可忽视的现象,但其研究相对比较滞后。本文主要介绍了汲取质反渗模型的研究进展,分析了渗透压差、膜表面流速、膜结构与膜材料、温度、汲取质种类、膜取向、离子水力半径等因素对汲取质反向渗透的影响情况,并发现汲取质的反向渗透通量可由其浓度或汲取液渗透压的一元多项式表达。总体而言,FO模式的汲取质反渗模型经过不断发展已相对比较完善,而压力阻尼渗透(PRO)模式的反渗模型则缺陷较大,有待进一步研究;此外,关于汲取质反渗过程影响因素及其影响机制的研究对于汲取质、膜材料的选择与开发,以及正渗透过程的优化均具有重要的指导作用,因此会引起越来越多的关注。     

PREDISPERSED SOLVENT EXTRACTION──THE STATE-OF-THE-ART REVIEW

Predispersed solvent extraction (PDSE) is a new extraction technique in which one of the two phases (usually the oil phase) is predispersed into minute droplets. The essential part of this novel technique is the use of colloidal liquid aphrons (CLA) together with colloidal gas aphrons (CGA). The use of colloidal liquid aphrons in predispersed solvent extraction may ameliorate the problems such as emulsion formation, reduction of interfacial mass transfer etc. In this paper, PDSE process, CLA and CGA are systematically reviewed and the potential applications of CLA, CGA and PDSE for the various areas of separation as well as the latest development in this area are discussed.