Investigation of the Different Regimes Associated with the Growth of an Interface at the Exit of a Capillary Tube into a Reservoir: Analytical Solutions and CFD Validation.

The emergence of a droplet from a capillary tube opening into a reservoir is an important phenomenon in several applications. In this work, we are particularly interested in this phenomenon in an attempt to highlight the physics behind droplet appearance. The emergence of a droplet from a tube opening into a reservoir under quasi-static conditions passes through three stages. The first stage starts when the meniscus in the tube reaches the exit. At this moment, the meniscus intersects the wall of the tube at the equilibrium contact angle. The interface then develops until its radius of curvature becomes equal to the tube radius. During this stage, the capillary pressure increases. In the second stage, the interface continues to evolve with its radius of curvature increasing until the static contact angle with respect to the surface of the reservoir is achieved. This marks the end of the second stage and the start of the third in which the contact line (CL) starts to depart the tube opening along the reservoir surface and the contact angle remains constant. Analytical models for the three stages have been derived based on the law of conservation of linear momentum. The models account for pressure, gravitational, capillary, and viscous forces, while inertia force is ignored. The model can predict the profiles of the mean velocity in the tube, the capillary pressure, and the evolution of the contact angle. In addition, a computational fluid dynamics (CFD) simulation has been conducted to provide a framework for validation and verification of the developed model. The CFD simulation shows qualitative behavior in terms of snapshots of the emerging droplet with time similar to that speculated by the analytical model. In addition, quantitative comparisons with respect to velocity, pressure, and volume profiles of the droplet show very good agreement, which builds confidence in the modeling approach.

Capillary-Driven Ejection of a Droplet from a Micropore into a Channel: A Theoretical Model and a Computational Fluid Dynamics Verification.

In this work, the problem of re-ejection of a permeating droplet through a membrane pore back to the feed channel when the transmembrane pressure (TMP) becomes zero is investigated. This problem is important in the context of oily water filtration using membranes. In particular, in the novel periodic feed pressure technique (PFPT), which has been proposed to combat membrane fouling, the TMP alternates between the operating value and zero in a periodic manner. During the period in which TMP is high, filtration occurs, and when it is zero, cleaning commences. We are particularly interested in what happens to a droplet, initially undergoing permeation, when the TMP becomes zero. It is evident that when the TMP is zero the meniscus inside the pore reverses its motion toward the feed channel rather than toward the permeate side by the action of interfacial tension force. A theoretical model is built to determine the rate at which the meniscus inside the pore advances when the TMP is zero. The conservation of momentum equation is used to establish a one-dimensional model that updates the location of the meniscus with time. The derived model considers both quasi-static and dynamic scenarios. In addition, the model accounts for both the viscosity contrast between the two fluids, as well as the gravity. A computational fluid dynamics (CFD) simulation has been built to provide a framework for model verification and validation. The model, based on quasi-static conditions, provides an overall similar trend to that obtained via CFD analysis. Nevertheless, the quasi-static model predicts a more rapid meniscus advancement inside the pore than the CFD simulation. When the dynamic contact angle is incorporated, very good matching is observed.

Magnetic γ-Fe2O3/ZIF-7 Composite Particles and Their Application for Oily Water Treatment.

Crude oil spills are about global challenges because of their destructive effects on aquatic life and the environment. The conventional technologies for cleaning crude oil spills need to study the selective separation of pollutants. The combination of magnetic materials and porous structures has been of considerable interest in separation studies. Here, γ-Fe2O3/ZIF-7 structures were prepared by growing a ZIF-7 layer onto supermagnetic γ-Fe2O3 nanoparticles with an average size of 18 ± 0.9 nm in situ without surface modification at low temperatures. The product composite particles were characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, vibrating sample magnetometry, and N2 adsorption/desorption isotherms. The analyses revealed a time growth-dependent ZIF-7 rod thickness with abundant nanocavities. The γ-Fe2O3/ZIF-7 surface area available for sorption (647 m2/g) is ∼12-fold higher than that of the γ-Fe2O3 nanoparticles. Moreover, the crystal structure of γ-Fe2O3 remained essentially unchanged following ZIF-7 coating, whereas the superparamagnetism declined depending on the coating time. The γ-Fe2O3/ZIF-7 particles were highly hydrophobic and selectively and rapidly (<5 min) sorbed crude oil and other hydrocarbon pollutants from water. As high as 6 g/g of the hydrocarbon was sorbed by the γ-Fe2O3/ZIF-7 particles immersed into the hydrocarbon. A coefficient of determination, R 2 2, consistently >0.96 at all pollutant concentrations suggested a pseudo-second-order sorption kinetics. The thermal stability and 15 cycles of use and reuse confirmed a robust γ-Fe2O3/ZIF-7 sorbent.

Conformance Control in Oil Reservoirs by Citric Acid-Coated Magnetite Nanoparticles.

Reservoir conformance control methods may significantly improve enhanced oil recovery technologies through reduced water production and profile correction. Excessive water production in oil and gas reservoirs leads to severe problems. Water shutoff and conformance control are, therefore, financially and environmentally advantageous for the petroleum industry. In this paper, water shutoff performance of citric acid-coated magnetite (CACM) and hematite nanoparticles (NPs) as well as polyacrylamide polymer solution in a heterogeneous and homogeneous two-dimensional micromodel is compared. A facile one-step technique is used to synthesize the CACM NPs. The NPs, which are reusable, easily prepared, and environmentally friendly, are characterized using Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, dynamic light scattering, and X-ray diffraction. The results confirm uniform spherical Fe3O4 NPs of an average diameter of 40 nm, well coated with citric acid. CACM NPs provide a high pressure drop coupled with an acceptable resistance factor and residual resistance factor owing to NP arrangement into a solid-/gel-like structure in the presence of a magnetic field. A resistance factor and a residual resistance factor of 3.5 and 2.14, respectively, were achieved for heavy oil and the heterogeneous micromodel. This structure contributed to an appreciable plugging efficiency. CACM NPs respond to ∼1000 G of magnetic field intensity and display a constant resistance factor at intensities between 4500 and 6000 G. CACM NPs act as a gel, forming a solid-/gel-like structure, which moves toward the magnetic field and thereby shuts off the produced water and increases the oil fraction. The findings of this study suggest the ability to shut off water production using specially designed magnetic field-responsive smart fluids. The application would require innovative design of field equipment.

Artificial Intelligence Based Methods for Asphaltenes Adsorption by Nanocomposites: Application of Group Method of Data Handling, Least Squares Support Vector Machine, and Artificial Neural Networks.

Asphaltenes deposition is considered a serious production problem. The literature does not include enough comprehensive studies on adsorption phenomenon involved in asphaltenes deposition utilizing inhibitors. In addition, effective protocols on handling asphaltenes deposition are still lacking. In this study, three efficient artificial intelligent models including group method of data handling (GMDH), least squares support vector machine (LSSVM), and artificial neural network (ANN) are proposed for estimating asphaltenes adsorption onto NiO/SAPO-5, NiO/ZSM-5, and NiO/AlPO-5 nanocomposites based on a databank of 252 points. Variables influencing asphaltenes adsorption include pH, temperature, amount of nanocomposites over asphaltenes initial concentration (D/C0), and nanocomposites characteristics such as BET surface area and volume of micropores. The models are also optimized using nine optimization techniques, namely coupled simulated annealing (CSA), genetic algorithm (GA), Bayesian regularization (BR), scaled conjugate gradient (SCG), ant colony optimization (ACO), Levenberg-Marquardt (LM), imperialistic competitive algorithm (ICA), Fletcher-Reeves update (CGF), and particle swarm optimization (PSO). According to the statistical analysis, the proposed RBF-ACO and LSSVM-CSA are the most accurate approaches that can predict asphaltenes adsorption with average absolute percent relative errors of 0.892 % and 0.94%, respectively. The sensitivity analysis shows that temperature has the most impact on asphaltenes adsorption from model oil solutions.

A review of polymer nanohybrids for oil recovery.

As oil fields go into their final stage of production, new technologies are necessary to sustain production and increase the recovery of the hydrocarbon. Chemical injection is an enhanced recovery technique, which focuses on increasing the effectiveness of waterfloods. However, the use of chemical flooding has been hampered by its relatively high cost and the adsorption of the injected chemicals onto the reservoir rocks. In recent years, nanofluids have been launched as an overall less expensive and more efficient alternative to other chemical agents. Nanoparticle inclusion is also proposed to mitigate polymer flooding performance limitations under harsh reservoir conditions. This review presents a comprehensive discussion of the most recent developments of polymer nanohybrids for oil recovery. First, the preparation methods of polymer nanohybrids are summarized and explained. Then, an explanation of the different mechanisms leading to improved oil recovery are highlighted. Finally, the current challenges and opportunities for future development and application of polymer nanohybrids for chemical flooding are identified.

Effect of Hydrophobic and Hydrophilic Metal Oxide Nanoparticles on the Performance of Xanthan Gum Solutions for Heavy Oil Recovery.

Recent studies revealed higher polymer flooding performance upon adding metal oxide nanoparticles (NPs) to acrylamide-based polymers during heavy oil recovery. The current study considers the effect of TiO2, Al2O3, in-situ prepared Fe(OH)3 and surface-modified SiO2 NPs on the performance of xanthan gum (XG) solutions to enhance heavy oil recovery. Surface modification of the SiO2 NPs was achieved by chemical grafting with 3-(methacryloyloxy)propyl]trimethoxysilane (MPS) and octyltriethoxysilane (OTES). The nanopolymer sols were characterized by their rheological properties and ζ-potential measurements. The efficiency of the nanopolymer sols in displacing oil was assessed using a linear sand-pack at 25 °C and two salinities (0.3 wt % and 1.0 wt % NaCl). The ζ-potential measurements showed that the NP dispersions in deionized (DI) water are unstable, but their colloidal stability improved in presence of XG. The addition of unmodified and modified SiO2 NPs increased the viscosity of the XG solution at all salinities. However, the high XG adsorption onto the surface of Fe(OH)3, Al2O3, and TiO2 NPs reduced the viscosity of the XG solution. Also, the NPs increased the cumulative oil recovery between 3% and 9%, and between 1% and 5% at 0 wt % and 0.3 wt % NaCl, respectively. At 1.0 wt % NaCl, the NPs reduced oil recovery by XG solution between 5% and 12%, except for Fe(OH)3 and TiO2 NPs. These NPs increased the oil recovery between 2% and 3% by virtue of reduced polymer adsorption caused by the alkalinity of the Fe(OH)3 and TiO2 nanopolymer sols.

Treatment of steam-assisted gravity drainage water using low coagulant dose and Fenton oxidation.

The use of coagulation and Fenton oxidation was studied for total organic carbon (TOC) and silica removal from steam-assisted gravity drainage (SAGD) water at 800C and two different concentrations replicating the stream feeding the warm lime softening unit having 675 mg/L TOC and 350 mg/L silica and the blowdown of the once through steam generator having 3700mg/L TOC and 2585 mg/L silica. Coagulation was carried out by the addition of FeCl3, Al(NO3)3 or Ca(NO3)2. The results showed that Fe(III) salt outperformed Al(III) and Ca(II) salts. A two-stage addition of 2.5 g FeCl3 per g TOC intermediated by a filtration unit resulted in approximately 72% TOC removal and more than 80% silica removal while maintaining low solid waste. Comparing results pertaining to coagulant concentration and final pH, it can be easily concluded that silica removal is governed by the resultant pH, whereas TOC removal was accomplished through surface neutralization and localized enmeshment coagulation. Fenton oxidation is proposed to further treat the filtrate obtained from the second stage Fe(III) coagulation. An additional 10% TOC removal could be achieved; at seven times lower H202 dose in the presence of Fe2+ or Fe0 reagent. Moreover, the advanced Fenton process resulted in high silica removal as a result of adsorption onto Fe(OH)3 precipitate, which formed at the equilibrium pH of the system.

Adsorption of asphaltenes from heavy oil onto in situ prepared NiO nanoparticles.

Removal of asphaltenes from heavy oil improves the quality of oil and makes it easier to process. To this end, Nassar et al. [1] recently showed that NiO nanoparticles have high affinity toward asphaltene adsorption. This investigation, however, involved toluene model solutions and commercially available nanoparticles. In the current work, we show that NiO nanoparticles prepared in situ within heavy oil display much higher affinity toward asphaltenes adsorption, and uptake in the order of 2.8 g asphaltene/g nanoparticles is reported. This uptake way exceeds asphaltene adsorption onto conventional porous adsorbents and commercial nanoparticles from toluene model solutions. Nanoparticle preparation followed a method developed by our group [2], and XRD, EDX, and TEM analyses confirmed the formation of NiO nanoparticles of 12±5 nm mean diameter. Kinetic experiments showed that, while equilibrium could be achieved in less than 2 h for both in situ prepared and commercial NiO particles, much higher adsorption took place onto the in situ prepared ones, owing to their better dispersion. Contrary to literature findings on adsorption from model solutions onto nanoparticles, surface coverage calculations revealed multilayer adsorption.

Produced water treatment by micellar-enhanced ultrafiltration.

A water treatment approach combining ultrafiltration (UF) and micellar-enhanced ultrafiltration (MEUF) techniques was used for the removal of organic contaminants in field produced water samples from Canada and the United States. Free oil droplets and suspended solids were separated by initial UF treatments while MEUF was necessary for the removal of dissolved organics. It was shown that the amphiphilic characteristics of some organics commonly existing in produced water contributed to lowering the critical micelle concentration (CMC) of the surfactant employed. Lower surfactant concentrations could, therefore, be employed leading to lower fouling and back contamination and higher permeate flux. In addition, the incorporation of organic contaminants into the structure of cetylpyridinium chloride (CPC) micelles resulted in larger size and higher dissolution capacity of the "mixed micelles". The performance of polymeric and ceramic membranes of different molecular weight cutoffs (MWCOs) was evaluated by analyzing the permeate flux, recovery ratio, and solute percent rejection as functions of trans-membrane pressure (TMP). A mathematical model based on Darcy's law and the resistance in-series model successfully described the flux decline as a function of TMP for the two field samples and the two membranes studied.

Scavenging H(2)S((g)) from oil phases by means of ultradispersed sorbents.

Ultradispersed catalysts significantly enhance rates of reaction and mass transfer by virtue of their extended and easy accessible surface. These attractive features were exploited in this study to effectively capture H(2)S((g)) from an oil phase by ultradispersed sorbents. Sorption of H(2)S((g)) from oil phases finds application for scavenging H(2)S((g)) forming during heavy oil extraction and upgrading. This preliminary investigation simulated heavy oil by (w/o) microemulsions having 1-methyl-naphthalene; a high boiling point hydrocarbon, as the continuous phase. H(2)S((g)) was bubbled through the microemulsions which contained the ultradispersed sorbents. The type and origin of sorbent were investigated by comparing in situ prepared FeOOH and commercial alpha-Fe(2)O(3) nanoparticles as well as aqueous FeCl(3) and NaOH solutions dispersed in the (w/o) microemulsions. The in situ prepared FeOOH nanoparticles captured H(2)S((g)) in a chemically inactive form and displayed the highest sorption rate and capacity. Temperature retarded the performance of FeOOH particles, while mixing had no significant effect.

Study and modeling of iron hydroxide nanoparticle uptake by AOT (w/o) microemulsions.

Control over nanoparticle size is a key factor which labels a given preparation technique successful. When organic reactions are mediated by ultradispersed catalysts, the concentration of the colloidal nanoparticle catalysts and their stability become key factors as well. In this study, variables affecting iron hydroxide nanoparticle size, stability, and maximum possible colloidal concentration in AOT/water/isooctane microemulsions were investigated. Iron hydroxide was prepared in single microemulsions by first solubilizing iron chloride powder in the water pools, followed by addition of aqueous NaOH. Upon addition of NaOH, Fe(OH)3 nanoparticles stabilized in the water pools formed in addition to bulk precipitate of Fe(OH)3. The time-invariant concentration of the stabilized Fe(OH)3 is defined as the nanoparticle uptake, and it corresponds to the maximum possible concentration of the colloidal nanoparticles. The effect of the following variables on the nanoparticle uptake and size distribution was investigated: mixing time; surfactant concentration; water to surfactant mole ratio; and the initial concentration of the precursor salt. At 300 rpm of mixing a constant uptake of iron hydroxide nanoparticles was achieved in about 2 h and further mixing had limited effect on the nanoparticle uptake and particle size. An optimum R was found for which a maximum nanoparticle uptake was obtained. Nanoparticle uptake increased linearly with the surfactant concentration and displayed a power function with the initial concentrations of the precursor salt. The surface area/g of the nanoparticles was much higher than literature values, however, following a trend opposite to that of the nanoparticle uptake. The surface area/unit volume of the microemulsion, on the other hand, followed the same trend as the nanoparticle uptake. The particle size increased as R and/or the surfactant concentration increased. A mathematical model based on correlations for water uptake by Winsor type II microemulsions accurately accounted for the effect of the aforementioned variables on the nanoparticle uptake.

Effect of microemulsion variables on copper oxide nanoparticle uptake by AOT microemulsions.

Ultradispersed metal oxide nanoparticles have applications as heterogeneous catalysts for organic reactions. Their catalytic activity depends primarily on their surface area, which in turn, is dictated by their size, colloidal concentration and stability. This work presents a microemulsion approach for in situ preparation of ultradispersed copper oxide nanoparticles and discusses the effect of different microemulsion variables on their stability and highest possible time-invariant colloidal concentration (nanoparticle uptake). In addition, a model which describes the effect of the relevant variables on the nanoparticle uptake is evaluated. The preparation technique involved solubilizing CuCl(2) in single microemulsions followed by direct addition of NaOH. Upon addition of NaOH, copper hydroxide nanoparticles stabilized in the water pools formed in addition to a bulk copper hydroxide precipitate at the bottom. The copper hydroxide nanoparticles transformed with time into copper oxide. After reaching a time-independent concentration, mixing had limited effect on the nanoparticle uptake and particle size. Particle size increased with increasing the surfactant concentration, concentration of the precursor salt, and water to surfactant mol ratio; while the nanoparticle uptake increased linearly with the surfactant concentration, displayed an optimum with R and a power function with the concentration of the precursor salt. Surface areas per gram of nanoparticles were much higher than literature values. Even though lower area per gram of nanoparticles was obtained at higher uptake, higher surface area per unit volume of the reverse micellar system was attained. A model based on water uptake by Wisor type II microemulsions, and previously used to describe iron oxide nanoparticle uptake by the same microemulsions, agreed well with the experimental results.

A novel approach for the preparation of AgBr nanoparticles from their bulk solid precursor using CTAB microemulsions.

Microemulsions are suitable reaction media to prepare a wide variety of nanoparticles and provide control over their sizes. However, as typically used, microemulsions limit rates of rapid reactions and suffer from low reactant solubilization capacity. This work presents a new application of a novel approach aimed at minimizing these limitations. This approach, which was previously applied for AgCl nanoparticle preparation, involves solubilization of a bulk silver halide in the form of higher halides, by means of reaction with the surfactant counterion of a microemulsion, and the reprecipitation of silver halide nanoparticles in the water pools of individual reverse micelles. CTAB microemulsions were employed because they possess a reactive counterion and are known to have a high solubilization capacity for ionic reactants. Despite their high solubilization capacity, CTAB microemulsions achieved lower nanoparticles uptake (molar concentration of the colloidal nanoparticles) for the same surfactant concentration when compared to our previous study. The effect of the following variables on the nanoparticle uptake and the particle size was investigated: (1) operation variables, including rate of mixing and temperature; and (2) microemulsion variables, including CTAB and n-butanol concentrations, and water-to-surfactant mole ratio, R. These variables provide a comprehensive test to the proposed mechanism and expose the role of the surfactant layer rigidity. The nanoparticle uptake increased as the rate of mixing, temperature, and CTAB concentration increased, and decreased as n-butanol concentration and R increased. High n-butanol concentration and R values reduced the effective surfactant concentration and contributed to less surfactant layer rigidity and to particle aggregation.

A novel method for the preparation of silver chloride nanoparticles starting from their solid powder using microemulsions.

A novel method of preparing AgCl nanoparticles by mixing AgCl powder and a microemulsion consisting of dioctyldimethylammonium chloride/n-decanol/water/isooctane is introduced. This new method was discovered during the preparation of AgCl nanoparticles in single microemulsions by direct reaction with the dioctyldimethylammonium chloride surfactant counterion. The effect of the following variables on the concentration of the colloidal AgCl nanoparticles (the nanoparticle uptake) and the particle size were studied: (1) operating variables, including mixing and temperature; and (2) microemulsion variables, including surfactant and cosurfactant concentration, and water to surfactant mole ratio. Manipulating these variables provides an insight into the role of the surfactant surface layer rigidity on the phenomenon. The results were explained by the effect of these variables on reaction rates and the colloidal nanoparticle stability. Mixing had a significant effect on the nanoparticle uptake. At 300 rpm an equilibrium AgCl nanoparticle uptake was achieved in about 1 h, while without mixing only 5% of the equilibrium value was reached even after 24 h. An optimum temperature was found for which a maximum nanoparticle uptake was obtained. At higher temperatures, the nanoparticle uptake declined. The nanoparticle uptake increased linearly with the surfactant concentration, and the particle size increased as well. A monotonic decrease in the nanoparticle uptake accompanied by an increase in the particle size was observed when increasing n-decanol concentration or the water to surfactant mole ratio.