Recent advances in the design and use of Pickering emulsions for wastewater treatment applications.

Pickering emulsions have recently emerged as versatile systems capable of targeting many applications of wastewater treatment. The unique properties, which include high emulsion stability, easy preparation, low toxicity, and stimuli-responsiveness, pave the way for advances in common pollutant control processes. This review aims to provide a comprehensive overview on different aspects in the Pickering emulsion design focusing on the key structural relations and their implications in specific applications. The first section is dedicated to the critical parameters governing the Pickering emulsion type, droplet size and stability. Furthermore, a section describing methods for demulsification and particle recovery is included, in which various stimuli have been explored. Finally, the most potent applications of Pickering emulsions such as photocatalytic degradation, adsorption, extraction, and separation of common wastewater pollutants are presented and discussed with a great deal of attention towards the efficacy, current limitations, and future potential. Recognizing the rise of innovative Pickering emulsion solutions is expected to induce profound effects facilitating the technology transfer to industrial processes.

Wettability effect on oil recovery using rock-structured microfluidics.

Surface wettability has a crucial impact on drop splashing, emulsion dynamics, slip flow for drag reduction, fluid-fluid displacement, and various microfluidic applications. Targeting enhanced oil recovery (EOR) applications, we experimentally investigate the effect of matrix wettability on the invasion morphology and sweep efficiency of viscous oil displaced by different aqueous floods using microfluidics, whose porous network mimics a sandstone structure. For comparison, systematic experiments of the same oil-flood pair are done in both hydrophilic and hydrophobic microfluidic chips. The results show that the hydrophilic microfluidic rock has a remarkable increase in oil recovery by a factor of ≈1.44, compared to the hydrophobic case. In addition, we observe a more pronounced lateral growth of the displacing pattern of aqueous flood for the hydrophilic surface. Finally, we quantitatively explain the increasing factor in the recovery rate and finger width for the hydrophilic vs. hydrophobic rock-liked porous networks by incorporating the contact angle into a scaling analysis.

A microfluidic study of oil displacement in porous media at elevated temperature and pressure.

Microfluidics methods offer possibilities for visual observations of oil recovery processes. Good control over test parameters also provides the opportunity to conduct tests that simulate representative reservoir conditions. This paper presents a setup and procedure development for microfluidic oil recovery tests at elevated temperature and pressure. Oil recovery factors and displacement patterns were determined in single- or two-step recovery tests using two crude oils, high salinity salt solutions and low salinity surfactant solutions. Neither the displacement pattern nor the recovery factor was significantly affected by the pressure range tested here. Increasing temperature affected the recovery factor significantly, but with opposite trends for the two tested crude oils. The difference was justified by changes in wettability alteration, due to variations in the amounts and structure of the acidic and basic oil fractions. Low salinity surfactant solutions enhanced the oil recovery for both oils.

Effect of Low-Molecular-Weight Alcohols on Emulsion Stabilization with Lignosulfonates.

Lignosulfonates are biobased surfactants and specialty chemicals, which are described as water-soluble polyelectrolyte macromolecules that are generated during the sulfite pulping of lignocellulose biomass. Due to their amphiphilic nature, lignosulfonates have made their way into various applications, such as plasticizers, dispersants, and suspension or emulsion stabilizer. The stabilization efficiency for oil-in-water emulsions is affected, among other aspects, by the presence of alcohols. Low-molecular-weight alcohols can improve the performance of lignosulfonates; however, the effects of such additive have not yet been fully explored. In this article, we hence studied emulsion stability in dependence of alcohol concentration and other parameters, such as salinity. One or two regions of improved stability were found, which occurred at approximately 0.001-0.01 M alcohol in water, and in some cases additionally at 1-3 M. The four lignosulfonate samples responded distinctly to the alcohol additives. Little difference was found for varying lignosulfonate concentration or the alcohol type, that is, methanol, ethanol, or 2-propanol. Adding ethanol at high salinity (720 mM NaCl) showed a destabilizing effect. A decrease in interfacial tension was noted when adding 1 M ethanol or more, but the surface pressure of lignosulfonates decreased progressively at 0.3 M ethanol and above. These effects are counteracting, which could explain why increasing alcohol concentration would either enhance or impair stability. Overall, emulsion stability was affected by concentration effects and not cosurfactant action of the alcohols. Composition changes can influence the dielectric properties of the bulk solvent, further affecting the anionic functional groups, which was evidenced by alcohol addition affecting the lignosulfonates with lower hydrophobicity more strongly and by ethanol exhibiting the destabilizing effect at high salinity. In conclusion, adding low-molecular-weight alcohols may hence influence the behavior of lignosulfonates and render them more accessible for interactions with hydrophobic interfaces.

Lignosulfonates in Crude Oil Processing: Interactions with Asphaltenes at the Oil/Water Interface and Screening of Potential Applications.

The goal of this article is to test the potential application of lignosulfonates (LSs) in crude oil production and processing. Three LS samples of varying hydrophobicity and average molecular weight were considered. First, the interfacial tension between brine and xylene and interfacial dilational rheology properties of LS samples were measured. It was found that the most surface-active LS sample has the lowest molecular weight in agreement with the results from the literature. In the presence of asphaltenes, all three LS samples were able to compete with asphaltenes, the most polar crude oil component, at the interface and form mixed LS-asphaltene interfaces. However, only the most surface-active LS sample among the three tested could fully desorb asphaltenes at the highest tested LS concentration (500 ppm). Second, three possible applications were screened. LSs were tested to prevent the formation of w/o crude oil emulsions or to break these. However, the opposite effect was observed, that is, stabilization of water-in-crude oil emulsions. The potential application of LS in produced water (PW) clarification was furthermore considered. The kinetics of PW clarification was found unaffected by the presence of LS, even at very high concentrations (1000 ppm). Finally, the potential of LS for enhanced oil recovery was assessed. The LS flood changed the surface wettability toward water wetness for one of the samples, yet LS injection did not recover additional oil beyond brine recovery. It was concluded that LS has interesting properties, such as the potential to compete with crude oil indigenous components at the oil/water interface. The stabilization action of LS was dominant over any destabilization effect, which led to the conclusion that LSs are more efficient for stabilizing emulsions rather than destabilizing.

Microfluidic testing of flocculants for produced water treatment: Comparison with other methodologies.

Flocculants are often added during produced water treatment to improve the crude oil droplet growth and separation from the water phase. Prior to use in the field, their performance is tested in laboratory conditions, typically with jar tests that require quite large volumes of sample. In this paper we present a microfluidic method as an alternative to study the efficiency of flocculants on enhancing coalescence between oil droplets. Two crude oil emulsions and four flocculants at different concentrations were tested. The new method is also compared to the more traditional techniques. An anionic flocculant showed the biggest improvement in separation for almost all systems. What is more, marked differences were observed between methods with static (bottle and turbidity tests) and dynamic test conditions (light scattering and microfluidics), where stabilization and dispersion effects were observed for the latter. The microfluidic methodology, with added benefits such as visualization, lower sample volumes and shorter measurement times, yielded similar trends as compared to other techniques. Overall, it was shown that microfluidics is a viable alternative to the standard tests.

Development of a Microfluidic Method to Study Enhanced Oil Recovery by Low Salinity Water Flooding.

Microfluidics is an appealing method to study processes at rock pore scale such as oil recovery because of the similar size range. It also offers several advantages over the conventional core flooding methodology, for example, easy cleaning and reuse of the same porous network chips or the option to visually track the process. In this study, the effects of injection rate, flood volume, micromodel structure, initial brine saturation, aging, oil type, brine concentration, and composition are systematically investigated. The recovery process is evaluated based on a series of images taken during the experiment. The remaining crude oil saturation reaches a steady state after injection of a few pore volumes of the brine flood. The higher the injection rate, the higher the emulsification and agitation, leading to unstable displacement. Low salinity brine recovered more oil than the high salinity brine. Aging, initial brine saturation, and the presence of divalent ions in the flood led to a decrease in the oil recovery. Most of the tests in this study showed viscous fingering. The analysis of the experimental parameters allowed to develop a reliable and repeatable procedure for microfluidic water flooding. With the method in place, the enhanced oil recovery test developed based on different variables showed an increase of up to 2% of the original oil in place at the tertiary stage.

Lignosulfonate Salt Tolerance and the Effect on Emulsion Stability.

In this article, we adapted and compared methods to assess lignosulfonates for technical applications. Salt-induced agglomeration and precipitation were studied via mechanical separation and subsequent UV spectrometry. The effect of lignosulfonates on emulsion stability was investigated in two steps: measuring the amount of oil separated after centrifugation and subjecting the remaining emulsion to shear in a rheometer. To complement the results, interfacial tension (IFT) was measured by the spinning drop technique, and the droplet size distribution was determined via a laser scattering technique. The observed trends in lignosulfonate salt tolerance and emulsion stabilization efficiency were opposite; that is, samples with low salt tolerance generally exhibited better emulsion stabilization and vice versa. This tendency was further matched by the hydrophobic characteristic of the lignosulfonates. The droplet size distributions of lignosulfonate-stabilized emulsions were similar. The effect of lignosulfonates on IFT depended on the oil phase and sample concentration. As a general trend, the IFT was lower for lignosulfonates with low average molecular weights. It was concluded that the adapted techniques allowed for detailed assessment of lignosulfonates with respect to salt tolerance and emulsion stabilization. In addition, it was found that the suitability for these applications can to some extent be predicted by the analytical data.

Colloid chemistry and experimental techniques for understanding fundamental behaviour of produced water in oil and gas production.

Due to increasing volumes of produced water and environmental concerns related to its discharge, water treatment has become a major challenge during the production of crude oil and natural gas. With continuously stricter regulations for discharging produced water to sea, the operators are obliged to look for ways to improve the treatment processes or re-use the water in a beneficial way, for example as a pressure support during oil recovery (produced water re-injection). To improve the knowledge of the underlying phenomena governing separation processes, detailed information of the composition and interfacial properties of produced water is undoubtedly useful and could provide valuable input for better understanding and improving separation models. This review article summarizes knowledge gained about produced water composition and the most common treatment technologies, which are later used to describe the fundamental phenomena occurring during separation. These colloidal interactions, such as coalescence of oil droplets, bubble-droplet attachment or partitioning of components between oil and water, are of crucial importance for the performance of various technologies and are sometimes overlooked in physical considerations of produced water treatment. The last part of the review deals with the experimental methodologies that are available to study these phenomena, provide data for models and support development of more efficient separation processes.

The effect of dissolved gas on coalescence of oil drops studied with microfluidics.

HYPOTHESIS: In literature it is stated that the stability of oil-in-water emulsions could be enhanced by decreasing the so-called "hydrophobic interactions" between surfaces through removal of dissolved atmospheric gases. Since the effect of the dissolved gases depends on the hydrophobicity of the oil phase, as well as the system pressure, we vary this effect systematically and monitor droplet coalescence in a tailor-made microfluidic device. EXPERIMENTS: The coalescence of oil drops in standard and degassed conditions was studied by direct observation using a microfluidic setup. Two model oils (heptane and xylene) were used to represent different hydrophobicity of the dispersed phases, together with an oil with dynamic interfacial behaviour (diluted crude oil). In addition, the effect of the volume fraction, droplet size and degassing method was studied. FINDINGS: At ambient pressure, the degassing of the continuous phase reduced the extent of coalescence for the model oils, which is in agreement with other reports. No effect of the dissolved gases was found on the drop formation process. At elevated pressures, the dissolved gases influenced only the most hydrophobic oil (heptane), while causing no effect in the other systems. The coalescence frequencies decreased upon the reduction of the drop sizes, which was justified with the theory for two interacting spheres.

Two-dimensional array of particles originating from dipole-dipole interaction as evidenced by potential curve measurements at vertical oil/water interfaces.

We propose a new method to evaluate the interaction potential energy between the particles adsorbed at an oil/water interface as a function of interparticle distance. The method is based on the measurement of the interparticle distance at a vertical oil/water interface, at which the gravitational force is naturally applied to compress the particle monolayer in the in-plane direction. We verified the method by examining whether we obtained the same potential curve upon varying the gravitational acceleration by tilting the interface. The present method is applicable in the force range from ∼0.1 to ∼100 pN, determined by the effective weight of the particles at the interface. The method gives a rather simple procedure to estimate a long range interaction among the particles adsorbed at oil/water interfaces. We applied this method to polystyrene particles at the decane/aqueous surfactant solution interface, and obtained the interparticle potential curves. All the potential curves obtained by the present method indicated that the interparticle repulsion is due to the electrical dipole-dipole interaction based on the negative charge of the particles. The mechanism of the dipole-dipole interaction is further discussed on the basis of the effects of surfactants.

Induction and coverage times for crude oil droplets spreading on air bubbles.

The interactions between crude oil droplets and air bubbles were studied by the droplet-bubble micromanipulator technique. Eight crude oils were investigated, and some aspects of the involved mechanisms were discussed. The induction time was measured for air bubbles approaching crude oil droplets in different aqueous phases. Distinct differences were observed in the presence and absence of salts, which showed the importance of long-ranged electrostatic repulsive forces on thin-film stability. The results also suggested that adsorption of dissolved hydrocarbons at air bubble surfaces may increase the potential energy barrier in the thin liquid film. Furthermore, the time needed for crude oil droplets to spread over the air bubble surfaces (referred to as coverage time) was determined for the crude oils. The results showed that the spreading velocity decreased with increasing viscosity of the crude oil. The detailed understanding of this type of interaction is considered to be a precursor for improving the oil removal efficiency during the flotation process.

Heavy crude oils/particle stabilized emulsions.

Fluid characterization is a key technology for success in process design for crude oil mixtures in the future offshore. In the present article modern methods have been developed and optimized for crude oil applications. The focus is on destabilization processes in w/o emulsions, such as creaming/sedimentation and flocculation/coalescence. In our work, the separation technology was based on improvement of current devices to promote coalescence of the emulsified systems. Stabilizing properties based on particles was given special attention. A variety of particles like silica nanoparticles (AEROSIL®), asphalthenes, wax (paraffin) were used. The behavior of these particles and corresponding emulsion systems was determined by use of modern analytical equipment, such as SARA fractionation, NIR, electro-coalescers (determine critical electric field), Langmuir technique, pedant drop technique, TG-QCM, AFM.

Stability of binary and ternary model oil-field particle suspensions: a multivariate analysis approach.

The transmission profiles of one- to three-component particle suspension mixtures were analyzed by multivariate methods such as principal component analysis (PCA) and partial least-squares regression (PLS). The particles mimic the solids present in oil-field-produced water. Kaolin and silica represent solids of reservoir origin, whereas FeS is the product of bacterial metabolic activities, and Fe(3)O(4) corrosion product (e.g., from pipelines). All particles were coated with crude oil surface active components to imitate particles in real systems. The effects of different variables (concentration, temperature, and coating) on the suspension stability were studied with Turbiscan LAb(Expert). The transmission profiles over 75 min represent the overall water quality, while the transmission during the first 15.5 min gives information for suspension behavior during a representative time period for the hold time in the separator. The behavior of the mixed particle suspensions was compared to that of the single particle suspensions and models describing the systems were built. The findings are summarized as follows: silica seems to dominate the mixture properties in the binary suspensions toward enhanced separation. For 75 min, temperature and concentration are the most significant, while for 15.5 min, concentration is the only significant variable. Models for prediction of transmission spectra from run parameters as well as particle type from transmission profiles (inverse calibration) give a reasonable description of the relationships. In ternary particle mixtures, silica is not dominant and for 75 min, the significant variables for mixture (temperature and coating) are more similar to single kaolin and FeS/Fe(3)O(4). On the other hand, for 15.5 min, the coating is the most significant and this is similar to one for silica (at 15.5 min). The model for prediction of transmission spectra from run parameters gives good estimates of the transmission profiles. Although the model for prediction of particle type from transmission parameters is able to predict some particles, further improvement is required before all particles are consistently correctly classified. Cross-validation was done for both models and estimation errors are reported.

Synthesis, functionalisation and characterisation of mesoporous materials and sol-gel glasses for applications in catalysis, adsorption and photonics.

In this review, synthesis and functionalisation approaches for ordered mesoporous materials and sol-gel glasses are described. Catalytic and adsorption applications are emphasised for the ordered mesoporous materials, while optical applications are the focus for sol-gel glasses.

Spectroscopic characterization of cobalt-containing mesoporous materials.

Cobalt-containing mesoporous materials that have been prepared using different procedures have been comparatively characterized by transmission electron microscopy/energy-dispersive X-ray spectroscopy (TEM/EDS), extended X-ray absorption fine structure spectroscopy (EXAFS), X-ray absorption near edge spectroscopy (XANES), and ultraviolet-visible (UV-vis), near-infrared (NIR), and mid-infrared (mid-IR) spectroscopies, and the results provide new insights into the local environment and properties of cobalt in this type of material. TEM/EDS analyses have shown that tetraethyl orthosilicate (TEOS) may be less appropriate as a silicon source during the syntheses of cobalt-containing mesoporous materials, because the distribution of cobalt throughout the framework may become uneven. EXAFS has been determined to be the most suitable method for direct verification of framework incorporation, by identifying silicon as the backscatterer in the second shell. Such a direct verification may not be obtained using UV-vis spectroscopy. From EXAFS analyses, it is also possible to distinguish between surface-bound and framework-incorporated cobalt. There is a good agreement between the results obtained from XANES and UV-vis regarding the coordination symmetry of cobalt in the samples. The presence of cobalt in the silica framework has been determined to create Lewis acid sites, and these acid sites are suggested to be located at tetrahedral cobalt sites at the surface.

Plasmachemical surface functionalised beads: versatile tailored supports for polymer assisted organic synthesis.

Plasmachemical surface modification of porous polystyrene beads with allylamine or diaminopropane provides reactive amine functionality exclusively at accessible surface sites, allowing faster reactions than classically prepared materials.