水包油型微乳液相色谱分离激素类药物的影响因素

采用水包油型微乳液相色谱(MELC)分离了6种激素类药物(醋酸可的松、泼尼松龙、己烯雌酚、炔雌醇、醋酸氟轻松及黄体酮)。考察了微乳流动相的组成成分(包括表面活性剂的浓度、油相种类、有机添加剂种类)及固定相孔径等对分离的影响。实验得到的最佳分离条件: 色谱柱为Venusil ASB C18 (T)(粒径5 μm,孔径30 nm,250 mm×4.6 mm),微乳流动相为30 g/L十二烷基硫酸钠(SDS)-0.8%正辛烷-6.6%正丁醇,流速为0.8 mL/min,检测波长为254 nm,柱温为35 ℃。该方法可用于甾体药物及其制剂的分离鉴别以及快速测定。     

乳状液膜法分离水中的铬

乳状液膜法由于其独特的物理化学性质,已广泛用于金属离子的萃取分离[1～3]。本文以span80-煤油-NaOH液膜体系分离水中铬。不加流动载体,利用内、外相中被分离物的浓度梯度实现物质迁移。当Cr2O2-7进入内相时,与内相的NaOH发生反应,在内相高浓度的NaOH存在下,可保持Cr2O2-7在液膜两侧有最大的浓度梯度,促使Cr2O2-7的迁移,实现Cr2O2-7与外相溶液的分离。1　实验部分1 1　仪器与试剂D40-1型电动搅拌器(杭州仪表电机厂),78-1型磁力加热搅拌器(江苏金坛新一佳仪器厂),721型分光光度计(上海第三分析仪器厂)。铬标准溶液(100ml/L):准…     

铜在乳状液膜体系中的迁移行为

近年来膜分离技术在环境治理方面得到广泛应用。本文研究了铜在span80-TBP（磷酸三丁酯）-煤油-NH3液膜分离体系中的迁移行为。用TBP作为载体,在溶液中迁移时,在外相与膜相界面上形成中性络合物后穿过膜相,在膜相与内相界面上络合物再与NH3反应,生成铜氨络离子,释放出来的TBP又返回膜相。     

Comparison of the separation of lactic acid and l-leucine by liquid emulsion membranes

A mass transfer model originally proposed for the permeation of zinc and l-phenylalanine was slightly modified and used for calculating the mass transfer resistances in lactic acid permeation (using the secondary amine Amberlite LA-2 as a carrier) and l-leucine permeation (using the quaternary ammoniumchloride Aliquat 336 as a carrier). The results show that under optimized conditions lactic acid permeation is controlled by the rate of reaction and that l-leucine permeation is controlled by the rate of reaction and the diffusion through the emulsion globule. The model results were compared with batch experiments separating lactic acid and l-leucine from real fermentation broths. The comparison shows that the separation rate is affected by co-transport of pH regulating agents and to a smaller extent by the co-transport of water.     

Physicochemical characterization of a modified cellulose acetate membrane for the design of oil-in-water emulsion disruption devices

In this paper, a new membrane separation process is presented. This process is based on a multiple chamber cell that allows the separation of oil from water by placing two membranes of different hydrophobicity in contact with the emulsion. Further chemical modifications of the membranes have been performed in order to vary their hydrophobicity in the perspective of optimizing the fractionation process via specific interactions between membrane and emulsion components. For this purpose, methylcellulose was modified with 1,2-epoxydodecane and incorporated in the membrane elaboration process. The modification of membrane surface chemical structure was demonstrated by ATR-FTIR and XPS experiments. Preliminary filtration tests are presented as well as future perspectives to optimize the membrane modification procedure.     

Process diagnosis of coalescence separation of oil-in-water emulsions-two case studies

Coalescence separation is a widely applied technology for oil/water emulsion separation. In this paper, we first review the existing coalescence theories regarding droplet capture, attachment and release. Two case studies are considered, dealing with the separation of oil-in-water emulsions using our recently developed coalescing filters. The first case (Case I) is associated with the separation of surfactant-stabilized hexadecane/water emulsions. The second case (Case II) addresses the separation of sulfonated kerosene/water emulsions in a continuous bench operation. In Case I, known wetting and collision theories were applied to understand the complex coalescence process occurring on the surface of the fibers. For this, the detrimental effect of surfactants on coalescence separation was taken into account. It was found that the best oil wetting coalescing material under water was not the most desired for coalescence, contradicting the existing theory. In addition, once the materials were pre-saturated with surfactant-containing emulsions, the oil wetting was enhanced significantly. However, the separation efficiency was maintained at the same level, unless the material adsorbed surfactant, resulting in minor reductions in the wetting angle. In Case II, based on the fiber properties and operation conditions, the droplet capture efficiency and released droplet size were calculated using the existing models. Fiber diameter and medium face velocity were found to affect not only the capture, but also drop release. Based on model predictions, the dominant capture mechanism was identified as interception followed by van der Waals forces. Overall, this work offers insights about the influencing parameters on oil/water emulsion separation for better designing coalescence systems.     

Effect and optimization of bed properties on water-in-oil emulsion separation

Water-in-oil emulsion separation through a fibrous media bed is a complex process in industries. In this article, in order to select the optimal fibrous material for the separation of water-oil emulsion, three types of commercial fibers as fibrous beds were used to separate water from diesel oil. Based on the principle of orthogonal experimental design, a series of experiments were performed to investigate the effect of such parameters as bed porosity (0.77-0.89), bed length (100-400?mm) and settlement length (120-480?mm) on the separation efficiency and the superficial velocity, and then three parameters were optimized to achieve good separation performance. The experiment showed that the separation efficiency could reach 77% and the flow velocity could reach 30?m/h under the optimal bed structure and stable working conditions. The results of this paper could provide basic designing reference for the industrial application of fibrous bed coalescer.     

Ultrafiltration of stable oil-in-water emulsion by polysulfone membrane

This paper focuses on treatment of oily wastewater coming out from the post-treatment unit of petroleum industries where finely divided oil droplets are uniformly dispersed in large volumes of water. Polysulfone (PSf) membranes which had been modified for higher porosity and hydrophilicity through the use of additives such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) were used for removal of oil from the oily wastewater. The performances of different PSf membranes were evaluated by treating with pure water as well as with laboratory made oil-in-water (o/w) emulsion. Experiments were carried out with 12 such membranes in a semi-batch filtration cell made of Teflon and the influence of operating conditions such as transmembrane pressure and feed properties such as initial oil concentration and pH of feed solution on membrane performance were investigated. Results show that all the parameters play a key role in permeate flux as well as percent oil separation. Also change in morphological properties of membranes due to addition of different molecular weight PVP and PEG are found to have a significant influence on the permeate flow rate and hence subsequent oil removal. The experimental results showed that oil retentions of almost all the membranes were over 90% and oil concentration in the permeate was below 10 mg/L, which met the requirement for discharge. It was concluded that the ultrafiltration (UF) membranes developed in the study were reasonably resistant to fouling and hence the developed PSf membranes may be considered feasible in treating oily wastewater.     

Film forming characteristics of oil-in-water emulsion with super-low oil concentration

The oil-in-water emulsion has been widely used as lubricant in metal working such as metal rolling and cutting. The film formation ability of emulsion was considered as an important evaluation factor. Thus the film formation mechanism and characteristics of emulsion have been widely investigated. However, the mechanism is still dubious and film forming characteristics were seldom discussed under an oil volume percentage of 0.05%. In this paper, a lubricating film testing apparatus is used to investigate the film forming characteristics of oil-in-water emulsion between the surface of a steel ball and that of a glass disc coated with chromium. By carrying out experiments under extremely low oil volume percentages (0.005–2.5%), some new phenomena are found in our program. The film formation mechanism of oil-in-water emulsion is discussed based on the different film forming performances of emulsion with different oil volume percentages. New viewpoints on the film formation of emulsion are put forward in this paper.     

Influence of HPAM on W/O emulsion separation properties

The present study reports on the influence of partially hydrolyzed polyacrylamide (HPAM) on essential w/o emulsion properties. The characterization has been undertaken with low field NMR to follow droplet sizes and distributions, sedimentation and coalescence kinetic, bench-scale electrocoalescence (E_crit) experiments to follow emulsion stability changes, and electrorheology to detect changes in the viscosity upon applying an external electric field. The result is that HPAM does not basically influence the droplet size distribution (DSD) and the stability level of the emulsions as can be expected of bulk polymers. However, there seems to be an interaction between added demulsifiers either through direct molecular interaction or via an interfacial complexation.     

Direct quantification of protein partitioning in oil-in-water emulsion by front-face fluorescence: avoiding the need for centrifugation

The quantification of proteins adsorbed at the oil-in-water interface is often difficult since it requires separation of fat globules from the aqueous phase that may damage the fat globule size and/or modify the interfacial composition. Front-face fluorescence spectroscopy was used to characterize the protein partitioning between the aqueous and oil phases of emulsions without separating these two phases. Different emulsions based on skim milk powder (SMP), two mono- and di-glyceride (MDG) mixtures (saturated and partially unsaturated), and three fats (hydrogenated and refined coconut oils and refined palm oil) were studied. The impact of an ageing period (24 h at 4 °C) was also investigated to typify the first step of ice cream processing. The emulsions were characterized for protein partitioning, immediately following emulsification and after ageing, using the Bradford spectrophotometric method, applied to the aqueous phase recovered after emulsion centrifugation. In parallel, the emulsions were characterized by their tryptophan emission fluorescence spectra. The area of the peaks at 333 nm, of the fourth-derivative fluorescence spectra corresponding to the amount of proteins present in the aqueous phase of emulsions, was well correlated with the Bradford measurements (r² = 0.91). This amount was also calculated from the fluorescence calibration curve obtained with SMP in solution. In conclusion, front-face fluorescence spectroscopy appeared to be a powerful and simple technique allowing the quantification of different populations of protein in an emulsified system, i.e., in the aqueous phase and loaded at the fat globule interface.     

Role of liquid crystal in the emulsification of a gel emulsion with high internal phase fraction

A gel emulsion with high internal oil phase volume fraction was formed via an inversion process induced by a water–oil ratio change. The process involved the formation of intermediate multiple emulsions prior to inversion. The multiple emulsions contain a liquid crystal formed by the surfactant with water; this was both predicted by the equilibrium phase diagram as well as observed using polarization microscopy. These multiple emulsions were more stable compared to alternative multiple emulsions prepared in the same way with a surfactant that does not form liquid crystals. While the formation of a stable intermediate multiple emulsion may not be a necessary condition for the inversion to occur, the transitional presence of a liquid crystal proved to be a significant factor in the stabilization of the intermediate multiple emulsions. The resulting gel emulsion contained a small fraction of the liquid crystal according to the phase diagram, and it exhibited excellent stability.     

Mathematical modeling of silver extraction by an emulsion liquid membrane process

A general physical model of a typical batch extraction system employing an emulsion liquid membrane process for the extraction of silver has been developed. The model takes into account the extraction reaction between the silver ion and the carrier molecules at the external interface, the diffusion of the complex in the membrane phase, the stripping reaction at the internal interface and the reaction of silver ion with the reagent, HCL, in the internal phase to yield silver chloride incapable of permeating through the membrane phase. In addition, the leakage of the internal aqueous phase to the external aqueous phase due to membrane breakage has been incorporated in this model. The batch extraction of silver using D2EHPA as a carrier has been carried out under various experimental conditions. The experimental data can be well explained by the present model.     

Preparation and characterisation of poly(high internal phase emulsion) methacrylate monoliths and their application as separation media

Poly(glycidyl methacrylate-co-ethyleneglycol dimethacrylate) monolithic supports were prepared by radical polymerisation of the continuous phase of water in oil high internal phase emulsions. Morphology of monolithic materials was studied by scanning electron microscopy and mercury intrusion porosimetry. The ratio of phase volume and the degree of crosslinking influenced the void size and pore size distribution of resulting polymers. Void sizes between 1 and 10 microm were observed and average pore sizes around 100 nm. Polymers with 60, 75, 80 and 90% pore volume were prepared and even samples with highest pore volume showed good mechanical stability. They were modified to bear weak-anion exchange groups and tested on the separation of standard protein mixture containing myoglobin, conalbumine and trypsin inhibitor. Good separation was obtained in a very short time similar to the separation obtained by commercial methacrylate monoliths. However, higher dispersion was observed. Bovine serum albumin dynamic binding capacity for monolith with 90% porosity was close to 9 mg/ml.     

Population Balance Model for Batch Gravity Separation of Crude Oil and Water Emulsions. Part I: Model Formulation

A population balance model for the separation of emulsions in a batch gravity settler is presented. Within the context of the model development, possible methodologies were elucidated for incorporating a) the physical properties of the bulk liquids, b) the physical properties of the phase interface, and c) the presence and functioning of interfacially active compounds. The model presented explicitly accounts for interfacial coalescence and the deformation of the emulsion zone due to the dynamic growth of the resolved dispersed phase; interfacial coalescence is modeled in terms of physically meaningful film drainage models and an approach for incorporating the accumulated buoyancy force in the dense packed layer is also discussed. Hydrodynamically hindered sedimentation is also considered in the model. The model is well suited to predict experimental batch settling data, especially data obtained from low-frequency NMR measurements of emulsion destabilization. The model predicts the evolution of the volume fraction of the dispersed phase at any axial position and time in the separator. Furthermore, the model predicts the location of the resolved dispersed phase interface as a function of time. Additionally, for any axial position and time in the settler, the model predicts the evolution of the average number density of droplets, the average volume/radius of droplets, the standard deviation of the droplet volume/radius, and the rate of growth of the droplets. The model is compared directly with experimental data for crude oil separations in Part II of this article.     

Model prediction of batch emulsion copolymerization as a function of conversion: A sensitivity analysis

Recently a model has been developed capable of predicting absolute monomer concentrations and their ratios in the polymer, aqueous, and monomer droplet phases as a function of conversion in batch emulsion copolymerizations without using any adjustable parameters. In this article the sensitivity of model predictions of composition drift toward deviations of 10% in all model parameters (maximum swellabilities of monomer in the polymer phase, water solubilities, reactivity ratios, and monomer and polymer densities) was estimated using the monomer combination methyl methacrylate-styrene as an example. From the sensitivity analysis it can be concluded that the reactivity ratios are the most important parameters affecting composition drift. The effects of deviations in maximum swellabilities and monomer and polymer densities on composition drift can be neglected, while the water solubility is important only in those cases where the amount of monomer in the aqueous phase cannot be neglected as compared with the total monomer amount. © 1994 John Wiley & Sons, Inc.     

Preparation of high molecular weight polyurethane particles by nonaqueous emulsion polyaddition

A versatile nonaqueous emulsion polyaddition process for the one-step fabrication of spherical polyurethane nanoparticles is presented. Three different emulsion systems were used consisting of N,N′-dimethylformamide (DMF) dispersed in n-hexane, acetonitrile dispersed in cyclohexane, and acetonitrile dispersed in tetradecane. After successful stabilization of the emulsion systems by using a poly(isoprene)-poly(methylmethacrylate) block copolymer, the fabrication of the polyurethanes was carried out within the dispersed polar phase. The polyurethane particles showed average diameters as small as 35 nm. Additionally, infrared (IR) characterization revealed that the formation of any urea, which decreases the mechanical properties of the polyurethanes, was prevented during the polyaddition. This was attributed to the anhydrous reaction conditions. Gel permeation chromatography (GPC) analysis demonstrated the average molecular weights (M _n) of the polyurethanes to be as high as 16,500 g/mol, corresponding to conversions of 0.98. Comparable molecular weights and conversions have not previously been achieved without the formation of urea.     

Selective separation of lambdacyhalothrin by porous/magnetic molecularly imprinted polymers prepared by Pickering emulsion polymerization

Porous/magnetic molecularly imprinted polymers (PM‐MIPs) were prepared by Pickering emulsion polymerization. The reaction was carried out in an oil/water emulsion using magnetic halloysite nanotubes as the stabilizer instead of a toxic surfactant. In the oil phase, the imprinting process was conducted by radical polymerization of functional and cross‐linked monomers, and porogen chloroform generated steam under the high reaction temperature, which resulted in some pores decorated with easily accessible molecular binding sites within the as‐made PM‐MIPs. The characterization demonstrated that the PM‐MIPs were porous and magnetic inorganic–polymer composite microparticles with magnetic sensitivity (M_s = 0.7448 emu/g), thermal stability (below 473 K) and magnetic stability (over the pH range of 2.0–8.0). The PM‐MIPs were used as a sorbent for the selective binding of lambdacyhalothrin (LC) and rapidly separated under an external magnetic field. The Freundlich isotherm model gave a good fit to the experimental data. The adsorption kinetics of the PM‐MIPs was well described by pseudo‐second‐order kinetics, indicating that the chemical process could be the rate‐limiting step in the adsorption of LC. The selective recognition experiments exhibited the outstanding selective adsorption effect of the PM‐MIPs for target LC. Moreover, the PM‐MIPs regeneration without significant loss in adsorption capacity was demonstrated by at least four repeated cycles.     

正十六胺为载体的乳状液膜迁移分离汞(Ⅱ)

以正十六胺为载体的乳状液膜迁移分离汞 的结果表明,当膜组成为(0 02～0 030)ｍｏｌ/Ｌ正十六胺+3%(Ｗ/Ｖ)Ｓｐａｎ80+煤油;内相为(0 010～0 020)ｍｏｌ/ＬＮａＯＨ;外相为0 020ｍｏｌ/ＬＫＣＬ+(0 010～0 10)ｍｏｌ/ＬＨＣｌ能使汞快速有效的完全迁移;并使Ｈｇ 与Ｃｕ ,Ｆｅ ,Ｚｎ ,Ｃｏ ,Ｎｉ ,Ｍｎ ,Ｐｂ ,Ｃｄ 等离子完全分离。不使用有毒害的膜溶剂甲秦或二甲苯[1-4],使用长碳链的有机胺,因而在相分离过程中避免了三相乳化现象。1.实验部分在制乳器中加入一定量Ｓｐａｎ80和正十六胺的煤油溶液,在约2000ｒ/ｍｉｎ转速下,加入内相试剂…     

Preparation of polymer particles having ethyleneurea groups at their surfaces by emulsifier-free seeded emulsion polymerization and wet adhesion of its emulsion film

Polymer emulsion having ethyleneurea groups at particle surfaces was produced by emulsifier-free seeded emulsion copolymerization of n-butyl methacrylate (BMA) and methacrylamide ethylethyleneurea (EU) with poly(BMA) seed particles utilizing the starved-fed monomer addition method. This emulsion film, prepared by casting the polymer emulsion on an alkyd resin plate, had a superior adhesion in water, as well as on stainless steel. Such superior wet adhesions seem to be based on a large amount of EU predominantly localized at the particle surfaces.Part CCXLIX of the series "Studies on suspension and emulsion"