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.     

Optimizing UPLC isocyanate determination through a Taguchi experimental design approach

The development of a chromatographic procedure for an ultra‐performance liquid chromatography can be a very time‐consuming task, as the general approach for finding the appropriate operating conditions has been a trial‐and‐error process. The present study reports a novel approach in the field of ultra‐performance liquid chromatography by using statistical experimental design based on Taguchi's method, which allows a complete separation of nine isocyanates present in a complex matrix. The resolution between two adjacent peaks was considered as a quality characteristic and transformed to a Taguchi signal‐to‐noise ratio. An orthogonal array L₉ (3⁴) was selected to analyze the effect of four chromatographic factors, that is, proportion of solvent, percent triethylamine (v/v), temperature (°C), and flow (mL min⁻¹), with three levels each. The joint analysis performed to the significant factors achieved in the eight analyses of variance allowed to identify two methods to conduct a complete separation of all peaks. Six isocyanates were separated with the first method, with all factors at the lowest level. The remaining three isocyanates were separated with the second method, with the proportion of solvent at the highest level and the other factors at the lowest level. The overall Taguchi experimental design identified the proportion of solvent and the flow rate as major chromatographic factors. Finally, confirmatory experiments were performed with samples prepared with six and three isocyanates, confirming the complete separation of all isocyanates in the study. The Taguchi methods provided a systematic and efficient methodology for this optimization, with considerably less effort than would be required for other optimizations techniques. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

An experimental investigation of creaming phenomenon using a novel optical method: A case study of mineral oil-in-water emulsion

The present study elucidates the creaming phenomenon of mineral oil-in-water macroemulsion using a new noninvasive method based on turbidimetry. Additionally, microscopic observation of the phenomenon is carried out to derive an in-depth understanding of the mechanisms. Accumulation of the particles in the emulsions under the formed cream is monitored during a relatively prolonged period of time. Backflow of continuous and dispersed phases in temporary channels is observed at the proximity of the cream. In addition to the backflow, a high traffic density of the dispersed particles and deflocculation of the cream are the main reasons for the accumulation of the dispersed phase particles and a temporary stability against creaming. The deflocculation hinders cream growth and increases the stratification of the cream. A low concentration zone of the dispersed phase with the width of ～100?µm is observed under the cream.     

Chemical destabilization of oil-in-water emulsion by novel polymerized diethanolamines

The main objective of this study was to synthesize novel demulsifiers for resolving oil-in-water emulsions. Diethanolamine polyethers are considered as a cationic polymer type. The study describes an improved synthesis of a series of diethanolamine polyethers via condensation of 3-7 or 9 mol of diethanolamine. The structure and the molecular weights of the major components in the reaction mixture were confirmed via IR and MS analyses. The demulsifiers were used for treatment of pollution in the refinery wastewater with or without FeCl3. The flocculation efficiency of the synthesized demulsifiers was determined by turbidity measurement of the treated and untreated O/W emulsion in the Cairo Oil Refinery Company. The critical flocculation concentration (CFC) and charge density of the synthesized demulsifiers were determined. Biodegradation of diethanolamine polyethers was measured in river water within 7-8 days.     

Behavior of soybean oil-in-water emulsion stabilized by nonionic surfactant

A soybean oil-in-water emulsion was prepared using nonionic Tween series surfactants. The effects of temperature, hydrophilic-lipophilic balance (HLB) value of the surfactant, and surfactant-to-oil ratio on the size of emulsion drops were investigated with an acoustic and electroacoustic devices. In the case of Tween 85, the influence of pH and electrolyte on the zeta potential of emulsion drops was examined. zeta potential appears to be strongly dependent on pH, varying in the case of high concentrations of NaCl from +60 to -90 mV. High concentrations of Na+ and K+ are capable of separating the oil phase from the emulsion. Divalent cations such as Ca2+ and Mg2+ lead to two points of zero charge at high concentrations, which is not observed for the case of hydrolyzable trivalent species like Al3+ and Fe3+.     

Synthesis of silica nanoparticles using oil-in-water emulsion and the porosity analysis

A set of silica particles was synthesized in oil–in–water emulsion with particle diameters ranging from ~42?nm to ~115?nm approximately. The porosity of the nanoparticles was analyzed using conventional nitrogen sorption and positron annihilation lifetime spectroscopy (PALS) techniques. The isotherm obtained using nitrogen sorption indicated that the particles were ‘non-porous?? however fitting data with Density Functional Theory model revealed a low concentration pore with diameters from 1.4?nm to 1.7?nm. The pore size was independent of the particle size. In contrast, analysis with PALS revealed a single pore size of ~0.6?nm present in all samples. Difference in results obtained for micropores <4?nm diameter is proposed to be dependent on models used and sample conditions for analysis.     

Demulsification of water-in-oil emulsion by using porous glass membrane

The hydrophilic porous glass membranes were used to demulsify water-in-oil emulsion, and demulsification efficiency can reach more than 96.2%. Effects of pore size of the membrane, transmembrane pressure and volumetric ratio of oil phase to internal aqueous phase in the emulsion on demulsification were investigated. It was found that pore size of membrane and transmembrane pressure can significantly affect demulsification efficiency. The smaller the pore size of the membrane, the better the demulsification efficiency. However, smaller pore size of the membrane has to be exerted a greater transmembrane pressure in order to make internal aqueous phase enter the membrane pore. Correspondingly, effect of transmembrane pressure on permeation flux of the droplets was also studied. In addition, recovered-oil phase by the demulsification were reused five times to extract cadmium from simulated aqueous waste. The results indicated that the extracting efficiency could arrive at 96.5%.     

Mechanism of demulsification of oil-in-water emulsion in the centrifuge

Summary The mechanism of demulsification of 30% Nujol-70 % water emulsions with various surfactants has been studied using a Coulter Counter to monitor the particle size at various depths in the cream layer as a function of time of centrifugation. It was found that the cream layer is stratified with varying sizes of oil globules along the centrifuge cell. Coalescence of the oil globules occurs throughout the body of the cream as well as at the bulk oil-cream interface at high concentrations of Tween 80, and Sponto 221 emulsions whereas the bulk oil-cream interface is found to be the major site of coalescence at lower concentrations of Tween 80 and Gantrez AN 119 emulsions. The globule size at the bulk oil-cream interface reaches a plateau (steady state particle size), and subsequently the rate of oil separation decreases considerably in all cases. The steady state particle size is a function of the concentration of Tween 80, the particle size increasing with increase in concentration of Tween 80.With 10 figures     

Polylactide hollow spheres fabricated by interfacial polymerization in an oil-in-water emulsion system

A one-step pathway has been adopted to fabricate biodegradable polylactide (PLA) hollow spheres by interfacial polymerization in an oil-in-water emulsion system. The mechanism of sphere formation is suggested with respect to interfacial cross-linking polymerization and subsequent precipitation of the unreacted PLA macromonomers onto the preformed shells. Their hollow nature and morphology were verified by transmission electron microscopy and scanning electron microscope characterizations.     

Ultrafiltration of soybean oil/hexane extract by porous ceramic membranes

This study investigated the ultrafiltration of soybean oil/hexane extract (miscella) using porous ceramic membrane. The evaporation energy can be saved in the soybean oil production by pre-separating a portion of hexane through the ceramic membrane. Raw soybean oil/hexane extract with 33 wt% of oil was used without pretreatment. A cross-flow ultrafiltration was performed using an anodisc membrane with a pore diameter of 0.02 μm and thickness of ∼1 μm. The concentrations of oil/hexane mixture were measured by UV adsorption at a wavelength of 458 nm. The separation mechanism was suggested to be the hindrance diffusion of soybean oil. Agitation in the feed side significantly increased the rejection of soybean oil. A small stage cut could also yield a higher rejection. Above observations were attributed to the reduction of concentration polarization by increasing the shear rate and small permeate flux, respectively. The optimum separation was achieved under the conditions of 4 kg/cm² transmembrane pressure, 0.04 stage cut and 120 rpm agitation speed. The concentration of soybean oil decreased from 33 wt% of feed to 27 wt% in permeate, that is, near 20% rejection. A gel-layer polarization model was proposed to estimate the gel concentration and thickness. The gel concentration was found 43–53 wt%. Agitating feed side reduced gel thickness, thus enhanced the rejection and permeate flux.     

Model for the prediction of separation profile of oil-in-water emulsion

This paper proposed a model that explains the separation mechanism of oil-in-water emulsion taking into account both creaming and coalescence processes. Oil-in-water emulsion separation experiments were performed in a batch separator using kerosene and distilled water. The predictions of the proposed model agreed well with the experimental results as well as previously published experimental data. The comparison between the proposed model and the previously published model showed that the proposed model has higher accuracy in predicting the separation profile of oil-in-water emulsion, with an accuracy of within 10%. Thus the proposed model gives better representation of the oil-in-water emulsion separation process.     

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.     

Optimization of polymeric triiodide membrane electrode based on clozapine-triiodide ion-pair using experimental design

Central composite design (CCD) and response surface methodology (RSM) were developed as experimental strategies for modeling and optimization of the influence of some variables on the performance of a new PVC membrane triiodide ion-selective electrode. This triiodide sensor is based on triiodide-clozapine ion-pair complexation. PVC, plasticizers, ion-pair amounts and pH were investigated as four variables to build a model to achieve the best Nernstian slope (59.9 mV) as response. The electrode is prepared by incorporating the ion-exchanger in PVC matrix plasticized with 2-nitrophenyl octal ether, which is directly coated on the surface of a graphite electrode. The influence of foreign ions on the electrode performance was also investigated. The optimized membranes demonstrate Nernstian response for triiodide ions over a wide linear range from 5.0 x 10(-6) to 1.0 x 10(-2)mol L(-1) with a limit of detection 2.0 x 10(-6) mol L(-1) at 25 degrees C. The electrodes could be used over a wide pH range 4-8, and have the advantages of easy to prepare, good selectivity and fast response time, long lifetime (over 3 months) and small interferences from hydrogen ion. The proposed electrode was successfully used as indicator electrode in potentiometric titration of triiodide ions and ascorbic acid.     

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.     

Formation and stability of paraffin oil-in-water nano-emulsions prepared by the emulsion inversion point method

Paraffin oil-in-water nano-emulsions stabilized by Tween 80/Span 80 were prepared using the emulsion inversion point method at different emulsification temperatures. Nano-emulsions with droplet size below 200 nm were formed above a critical surfactant-to-oil ratio of 0.20 at 50 degrees C. The main destabilization mechanism of the systems was found to be Ostwald ripening. An interesting phenomenon was that the Ostwald ripening rate declined as the surfactant concentration rose. Furthermore, flocculation was also found to contribute to the instability of the nano-emulsions, especially for those with low surfactant concentrations. Study on the electrophoretic properties of emulsion droplets revealed a negative value of the zeta potential, which was strongly dependent on the pH of the systems.     

Rapid development of the enantiomeric separation of beta-blockers by capillary electrophoresis using an experimental design approach.

A rapid method for determining the separation conditions for chiral resolution of eleven beta-blocking drug substances by capillary electrophoresis is described, using an experimental design approach. An acidic phosphate-triethanolamine buffer and an uncoated fused-silica capillary were used for all experiments. Several modified cyclodextrins were applied as chiral selectors: sulfobutyl ether beta-cyclodextrin (SBE-beta CD), dimethyl beta-cyclodextrin (DM-beta CD), carboxymethyl beta-cyclodextrin (CM-beta CD), and hydroxypropyl beta-cyclodextrin (HP-beta CD). Two different fractional factorial experimental designs were applied: (1) a design examining four factors at three levels (3(4-2)) and (2) one examining three factors at two levels (2(3-1)). The factors studied were: type of cyclodextrin, cyclodextrin concentration, pH of the background electrolyte and percentage of organic modifier. Enough resolution for the separation of the enantiomers and even for their quantification was reached. The same scheme is proposed when a fast chiral separation method needs to be developed for other drug families.     

A mechanistic study of photocyanation of pyrene in oil-in-water emulsion systems

A highly efficient one-step photocyanation reaction of pyrene was shown to proceed in oil-in-water emulsion systems. As a typical example, photoirradiation of pyrene in the presence of 1,4-dicyanobenzene and NaCN in a benzonitrile/water mixture (1/100, vol %) under vigorous stirring gave 1-cyanopyrene in a conversion yield of 83%, while an analogous reaction in an acetonitrile/water mixture (9/1, vol %) yielded this product in 61% yield. We evaluated the quantum yield of photocyanation in the oil-in-water emulsion system to be 0.17. Under optimum conditions, the quantum yield was improved to 0.68. Characteristics and possible mechanisms of the photocyanation reaction are discussed in detail.     

Macro-cellular silica foams: synthesis during the natural creaming process of an oil-in-water emulsion

The room-temperature synthesis of a macro-mesoporous silica material during the natural creaming process of an oil-in-water emulsion is reported. The material has 3-dimensional interconnected macropores with a strut-like structure similar to meso-cellular silica foams with mesoporous walls of worm-hole structure. The material has very high surface area (approximately 800 m2 g(-1)) with narrow mesopore size distribution.     

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…