Experimental Investigation on Yield Stress of Water-in-Heavy Crude Oil Emulsions in Order to Improve Pipeline Flow

An experimental study on yield stress of water-in-heavy crude oil emulsions has been carried out by using a HAAKE RS6000 Rheometer with a vane-type rotor. Several factors such as oil volume fraction, shear rate, temperature, and emulsifying agent on the yield stress of emulsions were investigated. Zero shear viscosity of heavy crude oil was 6000 mPas at 30°C, with a density 955 kg/m³. This study shows that the yield stress increases linearly with the increasing shear rate, and displays an exponential decay with increasing the temperature and oil volume fraction. Although the addition of emulsifying agent enhanced the stability of the emulsion, to some extent it also increased the yield stress, especially for the emulsions with high oil volume fractions. Therefore, to reduce the start-up force for the pipeline transport of water-in-heavy crude oil emulsions, the starting rate should be decreased, temperature increased, or oil volume fraction increased. These results are helpful to improve the transportation of water-in-heavy crude oil in pipeline.      

Experimental Investigation of Rheological and Morphological Properties of Water in Crude Oil Emulsions Stabilized by a Lipophilic Surfactant

Rheological behavior of two crude oils and their surfactant-stabilized emulsions with initial droplet sizes ranging from 0.5 to 75 µm were investigated at various temperatures under steady and dynamic shear testing conditions. In order to evaluate the morphology and Stability of emulsions, microscopic analysis was carried out over three months and average diameter and size distribution of dispersed droplets were determined. The water content and surfactant concentration ranged from 10 to 60% vol/vol and 0.1 to 10% wt/vol, respectively. The results indicated that the rheological properties and the physical structure and stability of emulsions were significantly influenced by the water content and surfactant concentration. The crude oils behaved as Newtonian fluids over a wide range of shear rates, whereas the emulsions behaved as non-Newtonian fluids, indicating shear-thinning effects over the entire range of shear rates. The viscosity, storage modulus and degree of elasticity were found to be significantly increased with the increase in water content and surfactant concentration. The maximum viscosity was observed at the point close to the phase inversion point where the emulsion system changes from water-in-oil emulsion to oil-in-water emulsion. The results also indicated that the rheological properties of crude oils and their emulsions are significantly temperature-dependent.     

Investigation of Oil–Asphaltene Slurry Rheological Behavior

The presence of asphaltene means additional difficulties related to transport and processing due to the increased crude oil viscosity caused by the asphaltene. For a better knowledge of the flow properties of asphaltene containing crude oils, it is necessary to understand how asphaltene affects the rheological properties. The aim of this article is to provide information on such rheological properties of oil–asphaltene slurry systems. The results of rheological experiments show that the non-Newtonian flow curves can be approximated by the Bingham plastic model to determine the apparent viscosity and the yield stress as a function of asphaltene concentration and temperature. An explanation is also provided for the observed behavior.     

Optimization of Process Parameters of Osthole-Loaded PLGA Microparticles Prepared Using Emulsification–Solvent Extraction

Osthole-loaded poly(d,l-lactic-co-glycolic) acid (PLGA) microparticles were prepared by oil-in-water (o/w) emulsification. The organic phase in emulsions was extracted by conventional evaporation and supercritical fluid extraction of emulsions. A Box–Behnken experimental design was used to evaluate the effects and to optimize the variables. Results indicated that the effects from two variables, that is, the emulsification stirring speed and the ratio of osthole to PLGA, had statistically significant on the encapsulation efficiency, while another variable, that is, the volume ratio of o/w, has no independent impact on the encapsulation. The interactions exist between the ratio of osthole to PLGA and the stirring speed, and between the volume ratio of o/w and the stirring speed. A second-order polynomial model was well adjusted to predict response variables, and 90.9% encapsulation efficiency could be realized at optimized conditions. The encapsulation efficiency of microparticles obtained with conventional evaporation was higher than that with supercritical fluid extraction of emulsions. The release curve of osthole from the microparticles could be nicely fitted by the Weibull equation and the release follows Fickian diffusion.     

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.     

Experimental Design Approach to Investigate the Effects of Operating Factors on the Surface Tension,Viscosity, and Stability of Heavy Crude Oil-in-Water Emulsions

In this article, the effects of various operating factors on the surface tension, viscosity, and stability of two heavy oil types in water emulsions for pipeline transportation are studied using the Taguchi experimental design approach. The surface tension of heavy crude oil-in-water emulsion is decreased by increasing the emulsifier concentration while the stability of emulsions is increased. The viscosity and stability are increased by an increase in oil content. An increase in the salinity and mixing speed leads to an increase in the stability of emulsion.     

An Experimental Study of Influence of Salt Concentration,Mixing Time,and pH on the Rheological Properties of Pre-Hydrated Bentonite Slurries Treated by Polymers

The aim of this study is to investigate the influence of pH between 8.5 and 12.5, mixing time, and of NaCl, KCl, and CaCl₂ concentration over the range of 0% to 20% on the rheological properties of pre-hydrated bentonite slurry following by treatments with different polymers. Viscometric data gathered by viscometer described well by the Herschel-Bulkley rheological model for all fluids tested. Increasing salt concentration and pH led to some significant changes in the rheological properties. Moreover, adding saturated salt to pre-hydrated slurry resulted in increasing shear stress and plastic viscosity for all fluids.     

Synergetic Effect of Reactive Surfactants and Clay Particles on Stabilization of Nonaqueous Oil-in-Oil (o/o) Emulsions

Although surfactants and particles are often used together in stabilization of aqueous emulsions, the contribution of each species to such stabilization at the oil-water interface is poorly understood. The situation becomes more complicated if we consider the nonaqueous oil-oil interface, i.e, the stabilization of nonaqueous oil-in-oil (o/o) emulsions by solid particles and reactive surfactants which, to our knowledge, has not been studied before. We have prepared Pickering nonaqueous simple (o/o) emulsions stabilized by a combination of kaolinite particles and a nonionic polymerizable surfactant Noigen RN10 (polyoxyethylene alkylphenyl ether). Different pairs of immiscible oils were used which gave different emulsion stabilities. Using kaolinite with equal volumes of paraffin oil/formamide system gave no stable emulsions at all concentrations while the addition of Noigen RN10 enhanced the emulsion stability. In contrast, addition of Noigen RN10 surfactant to silicon oil-in-glycerin emulsions stabilized by kaolinite resulted in destabilization of the system at all concentrations. For all systems studied here, no phase inversion in simple emulsion was observed by altering the volume fraction of the dispersed phase as compared to the known water-based simple Pickering emulsions.      

Stability and Rheological Properties of Model Low-Fat Salad Dressing Stabilized by Salep

A model low-fat salad dressing including salep as thickening agent was prepared. In order to obtain an stable salad dressing, different variables each one at three levels like salep content (0.5, 2.0, and 3.5% w/w), oil volume fraction (7.50, 16.25, and 25.00% w/w), pH (3, 5, and 7), salt concentration (0.3, 0.9, and 1.5% w/w), and egg yolk content (2, 4, and 6% w/w) were chosen and their effect on the creaming index of salad dressing was studied. It was observed that samples with highest salep content at pH 3 were the most stable during storage time (15 days). The microstructure of some samples was considered. Rheological measurements were performed for stable samples. Oil fraction and salt content increased zero shear viscosity and G′ modulus of samples.      

Stability and Rheological Properties of Suspended Pulp Particles Containing Orange Juice Stabilized by Gellan Gum

Gellan was used to suspend pulp particles in orange juice. Three groups of samples were prepared with 0%, 20%, and 40% orange juice concentrate and supplemented with gellan at different concentrations. A concentration-dependent increase in the size of gellan aggregates and gellan-protein assemblies was observed. Incorporation of gellan into the beverage with 0% juice concentrate changed the rheological behavior of sample to non-Newtonian shear-thinning fluid and increased its surface tension. When juice concentrate proportion was increased from 0% to 20%, the beverage viscosity increased. The highest gellan concentration resulted in a higher yield stress (σ₀) value and inhibited the pulp sedimentation completely.      

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.     

Demulsification Efficiency of Some New Demulsifiers Based on 1,3,5-Triethanolhexahydro-1,3,5-triazine

This study mainly concentrates on the synthesis of three novel demulsifiers and the investigation of their demulsification efficiency. The demulsifiers were derived from 1,3,5-triethanolhexahydro-1,3,5-triazine, which was prepared by the reaction of monoethanol amine with formaldehyde. The 1,3,5-triethanolhexahydro-1,3,5-triazine was ethoxylated by introducing 20 units of ethylene oxide and then esterified at different molar ratios with oleic acid (1, 2, and 3) to give three demulsifiers, namely, E₂₀TO, E₂₀TO₂, and E₂₀TO₃. The chemical structures of the prepared demulsifiers were confirmed by ¹H NMR and FTIR spectrum. The demulsification efficiency of these demulsifiers was tested on the natural water-in-oil (w/o) emulsions (50% water content). From the obtained results, it has been found that the investigated demulsifiers have a great potential to break the w/o emulsions. The trioleat ester (E₂₀TO₃) exhibited the maximum demulsification efficiency (96%) after 120 minutes at 55°C.     

Rheological Properties of Particle-Stabilized Emulsions

We have studied the rheological properties of fumed silica particle-stabilized emulsions. Two particles of different polarity were considered, the first more hydrophilic “Aerosil R7200,” the second more hydrophobic “Aerosil R972.” These particles flocculate and probably form a network at the investigated concentration. The flow curves of emulsions stabilized by a single type of particles exhibit yield stress, shear-thinning behavior and thixotropy. Moreover they display rheological features typical of gels. These features are attributed to strengthening of the particle network by droplets. Moreover the rheological properties of w/o emulsions stabilized by hydrophobic are similar to the ones of o/w emulsions stabilized by hydrophilic particles. The rheological properties of o/w emulsions stabilized by mixtures of hydrophilic and hydrophobic particles have then been studied by keeping the total particle concentration constant and varying the mass ratio between particles. The results show that when the hydrophobic particle concentration increases, the viscosity and stability of emulsions decrease establishing evidence that the network is weakened due to preferential orientation of hydrophobic particles towards the oil phase.     

Rheological Scaling Methods in Food Matrices Containing Stabilizer

Relative viscosity, Peclet, and Reynolds scaling methods were used in various food matrices consist of tragacanth gum (TG) (0.5, 1% wt), Oleic acid (5, 10% v/v) and WPI (2, 4% wt) and the best scaling law was selected. As these emulsions are non-Newtonian, they do not obey the usual, simple, scaling laws. When the apparent viscosity is reduced to relative viscosity of the medium at zero shear rate, a distinct reduced flow curve is obtained, regardless of TG, oleic acid, and WPI concentrations. This will lead to a technique of simplifying complex non-Newtonian flow curves and therefore predicting the rheological flow curves and fluid mechanics when different modifiers are added to food emulsions. The flow behavior of all samples was successfully modeled with the Cross model, Power law model, and Ellis model, and Power law model was found as the better model to describe the flow behavior of dispersions. Results showed that both G′ and G″ increased with TG, oleic acid and WPI concentrations. However, the viscoelastic behavior was mainly governed by the TG content.     

Strain-Dependent Rheological Model and Pressure Wave Prediction for Shut in and Restart of Waxy Oil Pipelines

Waxy oil gelation and rheology is investigated and modeled using strain-dependent viscosity correlations. Rotational rheometry shows a sharp viscosity increase upon gel formation. High creeping flow viscosities are observed at small deformation conditions prior to yielding. A new strain-dependent rheological model, following analogous formulation to the Carreau–Yasuda shear rate-dependent model, captures viscosity reduction associated with yielding. In addition, shear viscosity and extensional viscosity are investigated using a capillary rheometry method. Distinct shear-thinning behavior is observed in the shear mode of deformation, while distinct tension-thinning behavior is observed in the extensional mode of deformation for the model fluid systems. High Trouton ratios are obtained for the gelled model fluid systems, confirming strongly non-Newtonian fluid rheology. Finally, axial pressure wave profiles are computed at real pipeline dimensions for idealized moderate yield stress fluids using a computationally efficient 1D pipeline simulator. The Rønningsen time-dependent gel degradation model is used to emulate the fluid rheology in the simulator. Axial stress localization phenomena are shown to depend on the overall magnitude of gel degradation as established by the reduction in yield value. A high degree of gel degradation serves to afford flow commencement in a timely manner.     

Rheology and Structure of Cornstarch Suspensions in Water-Poly(propylene glycol) Mixtures

Concentrated aqueous cornstarch (CS) suspensions are often used to demonstrate an extreme example of shear thickening rheological behavior. Here, we describe the increased rheological complexity that occurs on the addition of poly(propylene glycol) (PPG) to an aqueous CS suspension. The appearance of shear thickening/jamming, shear thinning, yield stress and near-Newtonian behaviors is dependent on the PPG:water ratio. Rheological measurements have been complemented by dielectric measurements and optical microscopy. The complex behavior is interpreted in terms of reduced electrostatic stabilization of the CS particles with increased poly(propylene glycol) concentration. The analysis also suggests why cornstarch suspensions in water exhibit particularly good shear thickening characteristics.     

Multi-Walled Carbon Nanotubes as a Cosurfactant for Highly Concentrated Emulsions

The role of multi-wall carbon nanotubes (MWCNT) as a solid surfactant in highly concentrated water-in-oil emulsions was investigated. MWCNT were dispersed in the oil phase. These suspensions are viscoplastic fluids with the yield stress increasing by more than 1000 times with addition of 2% MWCNT, which demonstrates intensive “structurizing” ability. After emulsion preparation, MWCNT were concentrated at the interface, stabilizing emulsions. The dependence of the inversion point on MWCNT concentration was found. Emulsions containing up to 94 wt% of the aqueous phase can be prepared only when MWCNT is combined with conventional surfactant. Rheological properties of such compositions were measured. It was established that emulsions stabilized by a combined surfactant were more stable in comparison to conventional surfactant stabilized emulsion.     

Physical and Rheological Characteristics of Emulsion Model Structures Containing Iranian Tragacanth Gum and Oleic Acid

The physical and rheological properties of oil in water model emulsion systems containing Iranian tragacanth gum (TG) (0.5, 1 g/100 ml emulsions), whey protein isolate (WPI) (2, 4 g/100 ml emulsions), and oleic acid (5, 10 ml/100 ml emulsions) were investigated for droplet-size distribution, creaming index, and rheological properties of emulsions. The shear-thinning behavior of all dispersions was modeled using power law, Cross, and Ellis models. The power law model described the flow behavior of dispersions for its lowest standard error (0.29) and highest determination coefficient (R²) (0.99). Rheological investigation showed that both loss (G″) and storage (G′) modules increased as gum and oil content increased. Delta degree was 0.1 and increased as frequency increased, indicating that liquid-like viscose behavior dominated solid-like elastic behavior. Droplet-size distribution was measured by light scattering and microscopic observations revealed a flocculated system. Gum, WPI, and oil contents decreased the emulsion creaming index with gum concentration having the greatest effect.