Investigation of the Demulsification Efficiency of Some Ethoxylated Polyalkylphenol Formaldehydes Based on Locally Obtained Materials to Resolve Water-in-Oil Emulsions

Fourteen ethoxylated polyalkylphenol formaldehyde surfactants were prepared from locally sourced raw materials. These surfactants were used as demulsifiers to resolve asphltenic crude oil emulsions. Different factors affecting demulsification efficiency such as water:oil ratios, surfactant concentration, surfactant molecular weight, ethylene oxide content, alkyl chain length, and asphaltene content were investigated. From the data obtained it was found that the demulsification efficiency increases by increasing the concentration, alkyl chain length and water content in the emulsion. Also it was found that the increase of asphaltene content in the crude oil impeded the demulsification efficiency. The effect of molecular weight was studied and it was found that the demulsification efficiency was controlled by an optimum range of molecular weight between 3640 to 3810 for the family of demulsifiers studied. Regarding the effect of ethylene oxide content in the demulsifier structure, it was found that the maximum demulsification efficiency was obtaind at 40 units ethylene oxide. The maximum demulsification efficiency was obtained by TND5 (m.wt. = 3800, eo = 40 units). With this demulsifier 100% water separation was exhibited after 35 minutes at 150 ppm demulsifier concentration and 50% w/o emulsion. The surface, interfacial tension, and hydrophilic lipophilic balance (HLB) of the invistigated demulsifers were studied. The obtained results justified that they are strongly related to the demulsification effeciency.     

Characterization of Optical Properties in Water-in-Oil Emulsion

There have been few studies on the factors that determine the overall appearance of emulsions. Optical properties are quite important in determining the perceived quality of emulsion-based products. The overall appearance of an emulsion is determined by the way that it interacts with electromagnetic radiation in the visible region of the spectrum, for example, reflection, transmission, adsorption, and scattering. These interactions are principally determined by the characteristics of emulsion droplets (size, concentration, and refractive index). The present study aims at characterizing the optical properties and rheological behaviors of water-in-oil emulsions, especially macroemulsions. There is a decrease in the absorbance spectra as increasing glycerin ratio in aqueous phase because the difference of refractive index between oil phase and aqueous phase decreased, which improved the transparency of water-in-oil emulsion. The absorbance of linear and branched surfactant emulsions were smaller than that of alkyl modified branched surfactant emulsion. Moreover the transparency of emulsions prepared with linear and branched surfactants was much clearer than that of alkyl modified branched surfactant emulsion. The absorbance spectra also showed that low polar oil attributed to the more transparent emulsion, compared with high polar or nonpolar oil. However, these kinds of oils were not helpful to prepare transparent emulsion because the appearance of these emulsions was translucent or opaque, even if polyols in aqueous phase was 30 wt%.     

Fabrication of Porous Titania Particles from Water-in-Oil Emulsions for the Applications of Photocatalyst

In this study, polystyrene nanospheres were synthesized by dispersion polymerization using batch-type reactor for the self-organization with precursor materials inside emulsion droplets. Mechanical homogenization was applied for the emulsification of the polymeric nanospheres and titanium diisopropoxide bis (acetylacetonate) to produce the macroporous titania particles by evaporation-driven self-assembly. Similarly, spherical titania crystallites could be synthesized via self-organization using triblock copolymer instead of polymeric latex beads after successive calcination. The morphologies of the porous particles were observed using electron microscope, and the crystallinity of the porous titania particles was analyzed by powder x-ray diffraction. As a demonstrative application, the macroporous titania microparticles with anatase phase were adopted as photocatalyst for the decomposition of Rhodamine B, and excellent catalytic performance was observed with higher rate constant compared to the result from commercial titania nanocolloid. Collectively, our macroporous titania microparticles were found to be safe catalytic materials for human body minimizing the skin toxicity since the size of the catalysts is in the micron-range.     

An Experimental Study on the Viscosity of Water-in-Oil Emulsions

Water-in-oil (W/O) emulsions are very common in the petroleum industry, and their viscosities are the principle parameters for the operation design. Typical correlations composed by one or two factors cannot always fit the apparent viscosity of W/O emulsions very well, especially when applied to the crude oil/water emulsions. The viscosities of W/O emulsions, which were made from three kinds of crude oil, were measured by Anton Paar MCR302 viscometer at atmospheric pressure with different temperatures as well as shear rates. The experiment results indicate that W/O emulsion would exhibit Newtonian characteristic when water content is no higher than 0.2 and non-Newtonian characteristic otherwise. According to the experimental data, a modified correlation based on the Broughton–Squires model and Ronningsen model was introduced to predict the viscosity of W/O emulsions, and the comparison results showed that the new modified correlation has better accuracy than the original models.     

Microwave-Assisted Chemical Demulsification of Water-in-Crude-Oil Emulsions

Two case studies are presented that shows the effects of chemical demulsifiers used under conventional heating and in combination with microwave radiation on efficiency of demulsification and light transmittance of the water separated from the emulsions. The data shows that the chemical demulsifiers coupling with microwave radiation does a better job at demulsifying the water-in-crude-oil emulsions than when the chemical demulsifiers are used under conventional heating. The demulsification efficiency of AE-121 could reach 100% under microwave irradiation (300 W) for 50 seconds.     

Influence of Oil Content in Paraffins on the Behavior of Wax Emulsions: Wetting and Rheology

In this study, effect and correlation of alkyl chain length (C8, C10, C12, C14, and C16) and concentration of n-alkyl sulfate acid used as representative Br?nsted acid-combined-surfactant catalysts on dehydration esterification of oleic acid with 1-octanol as typical substrates are researched. CMC of the series surfactant are measured by surface tension method. The results indicate that alkyl chain length as well as concentration of catalyst plays an important role in determining conversion of esterifications. Appropriate chain length surfactant and concentration should be chosen for the combined-surfactant catalyzed reaction.     

Influence of Mixing Speed in Liquid Crystal Formation and Rheology of O/W Emulsions Containing Vegetable Oils

The process parameters are important in the development of emulsions containing liquid crystals. Thus, we studied the influence of the mixing speed in microscopic and rheological features. Oil-in-water emulsions using vegetable oils and nonionic surfactant were developed employing gradual raise of the mixing speed. It decreased the liquid crystal formation and the density values, and increased apparent viscosity values. The most suitable mixing speed was 600 rpm, since it allowed the attainment of emulsion with better performance and presence of lamellar liquid crystals. However, all emulsions were stable in these experimental conditions and presented pseudoplastic behavior and tixotropy.     

Enhanced sedimentation and coalescence of petroleum crude oil emulsions by the new generation of environmentally friendly yellow chemicals

This study compares by means of new and advanced destabilization protocols the efficiency of new chemistry environmentally friendly (yellow) demulsifiers with already commercially available red demulsifiers in destabilizing two types of water-in-oil (w/o) emulsions: petroleum crude oil emulsions and model dense packed layers (DPLs). Oil–water separation profiles were measured by low-field nuclear magnetic resonance (NMR), which allows monitoring the water content as well as the mean droplet size in the emulsion as function of the sample height and the time. Separation profiles measured by NMR depicted an increase of the free water release kinetics as the concentration of demulsifier as well as the sedimentation rate increased. The water resolution was not substantially improved by increasing the concentration further while the water quality was worse, most likely due to adsolubilization. There was no observation of DPL formation in these crude oil emulsions. Four different demulsifiers were tested on a model DPL and compared with normal crude oil emulsions. One chemical showed higher efficiency in destabilizing DPL than destabilizing crude oil emulsion. The interfacial rheological properties for one of the systems showed a slight increase in the elastic modulus (E′), as the concentration of demulsifier increased. The increment of the elastic modulus is not totally understood. The most central parameters were represented by principal component analysis (PCA). PCA did not contribute in a better characterization of the chemicals. The new-generation yellow demulsifiers did not reproduce the efficiency of commercially available, less environmentally friendly, (red) demulsifiers.     

Comparison of the Rheological Behavior of Solutions and Formulated Oil-in-Water Emulsions Containing Carboxymethylcellulose (CMC)

In this study, it was aimed to compare the rheological properties of carboxymethylcellulose (CMC) in aqueous solutions and their corresponding emulsions containing 0.05, 0.1, 0.25, and 0.5% CMC in the aqueous phase. Samples with 0.05 and 0.1% CMC showed Newtonian behavior, but shear-thinning behavior was observed in CMC solutions and emulsions with increasing CMC concentrations to 0.25% and 0.5%. Rheological behavior of all samples were modeled by Power law (R ² = 0.986–197) and Casson models (R ² = 0.968–1). According to the Ostwald–de Waele model, the consistency index of all samples was increased and the flow behavior index decreased with increasing CMC concentration. Comparison of our data with four predicting models (Einstein, Larson, Pal, and Dougherty-Krieger equations) showed that the viscosity of continuous phase controls the viscosity of emulsions with high CMC concentrations and these models are not applicable for such situations. Addition of CMC increased the emulsion stability of O/W emulsions. This stability was increased with increasing CMC concentrations.     

Formulation,Rheology, and Hypolepidemic Activity of Vegetable Oil-Based Eggless and Low-Fat Food Emulsions

Common edible oils such as almond, safflower, soybean, and mustard oil were formulated in the form of eggless and low-fat oil-in-water emulsions using a blend of nonionic emulsifier Glycerol monostearate and amphoteric emulsifier soy lecithin. The emulsion parameters such as vegetable oil, emulsifier, additive content and hydrophilic-lipophilic balance number of emulsifier were optimized. The storage stability of formulated emulsions was monitored under accelerated storage stability conditions for six months. Rheological characterization of stable emulsion revealed pseudoplastic flow behavior. In vivo hypolepidemic activity of formulated emulsions in rats showed considerable reduction in total cholesterol and triglyceride level after 14 days as compared with the marketed product. The almond oil emulsion is found superior than safflower oil emulsion.     

Synthesis and Rheology of Intercalated Polystyrene/Na+‐Montmorillonite Nanocomposites

Polystyrene (PS)/clay nanocomposites were synthesized by the emulsion polymerization of styrene in the presence of sodium ion‐exchanged montmorillonite (Na⁺‐MMT), demonstrating that the strongly hydrophobic PS was intercalated into the hydrophilic silicate layers. The nanocomposites were examined by means of X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis. The rheological properties of the PS/Na⁺‐MMT nanocomposites were also studied to exhibit more pronounced shear thinning behavior with increasing clay content.     

不同尺寸单分散PMMA/GMA/DVB聚合物荧光微球的制备

采用无皂乳液聚合及种子无皂乳液聚合方法制备了200～800 nm四种不同尺寸的单分散PMMA/GMA/DVB (PMGD)复合微球. 用扫描电镜(SEM)和动态光散射(DLS)对粒径尺寸、形貌进行了表征. 实验发现单体滴加速度是影响种子无皂乳液聚合过程二次成核的关键因素. 用乙二胺对微球表面的环氧基团开环后, 通过在微球表面接枝树枝状PAMAM (d-PAMAM)达到微球表面的官能化的目的, 元素分析和红外光谱实验证明了微球表面d-PAMAM的存在. 最后利用微球表面的活性氨基与四甲基异硫氰酸罗丹明(TRITC)反应, 得到四种尺寸的水分散性的红色荧光微球.     

Effect of Emulsifier Type on the Characterization of O/W Emulsions Using a Spectroscopy Technique

The droplet size distribution (DSD) of emulsions is the result of two competitive effects that take place during emulsification process, i.e., drop breakup and drop coalescence, and it is influenced by the formulation and composition variables, i.e., nature and amount of emulsifier, mixing characteristics, and emulsion preparation, all of which affect the emulsion stability. The aim of this study is to characterize oil-in-water (O/W) emulsions (droplet size and stability) in terms of surfactant concentration and surfactant composition (sodium dodecyl benzene sulphonate (SDBS)/Tween 80 mixture). Ultraviolet-visible (UV-vis) transmission spectroscopy has been applied to obtain droplet size and stability of the emulsions and the verification of emulsion stability with the relative cleared volume technique (time required for a certain amount of emulsion to separate as a cleared phase). It is demonstrated that the DSD of the emulsions is a function of the oil concentration and the surfactant composition with higher stability for emulsions prepared with higher SDBS ratio and lower relative cleared volume with the time. Results also show that smaller oil droplets are generated with increasing Tween 80 ratio and emulsifier concentration.     

Characterization of Monomer Emulsions in Terms of Droplet Size and Stability: Effect of Emulsifier Concentration

In emulsification processes, the estimation of the droplet size distribution is important data not only because it is linked with the manufacturing process, but also because it is an important parameter affecting the emulsion stability. The aim of this research is to use the ultraviolet-visible transmission spectrum as a tool for emulsion characterization (droplet size and stability) to be a function of monomer concentration, and to verify of emulsion stability using the volume of separated phase's technique. Both techniques are applied to monomer emulsions as a function of emulsifier concentration. Results show correlations between droplet size measurements and stability of emulsions using the spectroscopy technique; results were also found to be in agreement using the cleared volume method.     

Rheology of concentrated blends with immiscible components

The rheology and morphology evolution of nondilute and concentrated immiscible blends were investigated in this paper. A theoretical model was established by a Hamiltonian formalism. The interactions between droplets were integrated in the morphology‐dependent drag coefficient. The phenomenological parameters in the model were determined by the comparisons with the dilute emulsion model and the Krieger–Dougherty model. The model showed better predictions in the shear viscosity and first normal stress difference than that of the dilute emulsion model. The effects of volume fraction on droplet deformation were also predicted and compared with the numerical simulations. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2534–2540, 2005     

Drop Size Distribution of O/W Emulsions by Drop Immobilization with Agarose

ABSTRACT

A method for the determination of the drop size distribution of oil-in-water (O/W) emulsions is presented. Water-based coolant emulsions used in rolling mill operations were studied. The emulsions were gelled in agarose so that the oil droplets were immobilized and samples of these gels were measured by confocal laser scanning microscopy (CLSM) and image processing. The influence of the addition of CaCl₂ as an emulsion destabilizer on the size distributions was also studied. The experimental data obtained were compared to those obtained using photon correlation spectroscopy (PCS).     

Attainment of Emulsions with Liquid Crystal from Marigold Oil Using the Required HLB Method

Development of new formulations for topical use and cosmetic and pharmaceutical delivery agents has increased the complexity of emulsified systems. Liquid crystals, known since the nineteenth century are the third phase of an emulsion, being responsible for increasing its stability and the solubility of substances poorly soluble in water, or the oily phase, modulating the release of drugs imprisoned in its structure and promoting hydration of the skin surface. In the present work we developed oil/water emulsions, making use of Marigold oil (Calendula officinalis L) and ethoxylated fat alcohols as surfactant. The required HLB value for marigold oil was determined to be 6.0. The surfactants were associated in lipophilic/hydrophilic pairs. The lipophilic surfactants were Ceteth‐2 and Steareth‐2 and the hydrophilic surfactants were Steareth‐20, Ceteareth‐20, Ceteareth‐5, and Ceteth‐10. To identify the liquid crystalline phases, the emulsions were analyzed by polarized light microscopy. The physical stability was evaluated by rheology and zeta potential analysis. All emulsions presented lamellar liquid crystal structures. Results showed that this type of surfactant is able to produce liquid crystal in the system, with slight difference in appearance, influencing the physical stability, according to the methods applied.     

Controllable Preparation of Monodisperse Polystyrene Microspheres with Different Sizes by Dispersion Polymerization

Summary: Monodisperse polystyrene (PS) microspheres with different sizes were prepared by dispersion polymerization in dispersion media of ethanol/water and isopropayl alcohol/water, respectively. The effect of polarity of the dispersion medium, stabilizer and initiator concentration on the average sizes and size range were evaluated. The results show that monodisperse PS microspheres with different sizes could be prepared in dispersion media of ethanol and isopropyl alcohol/water when appropriate initiator and stabilizer concentrations were employed, and the latter is a more appropriate medium to prepare uniform PS microspheres. It was found that the microsphere sizes reduced with increasing water content in the dispersion medium. Furthermore, in isopropyl alcohol/water dispersions, the average sizes decreased with increasing stabilizer concentration.     

不同形态双金属氢氧化物颗粒水分散体系及其稳定的Pickering乳液

采用共沉淀法制备了3种形态的MgAl双金属氢氧化物颗粒的水分散体系, 并以其为乳化剂制备了Pickering乳液. 比较了3种颗粒的分散体系及其稳定的Pickering乳液的性质. X射线衍射(XRD)和透射电子显微镜(TEM)表征结果表明, 低结晶度的颗粒以形状不规则、 结构疏松、 表面粗糙的絮状体形式分散于水中, 且颗粒尺寸随高速搅拌分散时间的延长而减小; 而良好结晶的颗粒以形状规则、 结构致密、 表面平滑的六角片存在于水中. Zeta电位测试表明, 3种颗粒在水中均带正电荷, NaCl可降低颗粒的Zeta电位而使其发生絮凝, 但良好结晶颗粒的分散体系在更高NaCl浓度时才出现明显沉淀. 分别采用3种双金属氢氧化物颗粒/NaCl水分散体系制备了水包油(O/W)型Pickering乳液, 并比较了乳液的稳定性. 结果表明, NaCl的引入在一定程度上可提高3类乳液的稳定性; 良好结晶颗粒稳定乳液的能力强于低结晶度的颗粒; 对于低结晶度颗粒, 大颗粒稳定乳液的能力比小颗粒更强.