Dewetting dynamics of heavy crude oil droplet in low-salinity fluids at elevated pressures and temperatures.

HYPOTHESIS: Improved oil recovery by low-salinity injection correlates to the optimal brine concentration to achieve maximum dewetting of oil droplets on rock surfaces. While interfacial tension and electrical double layer forces are often cited as being determinant properties, we hypothesize that other structural/interfacial forces are more prominent in governing the system behavior. EXPERIMENTS: The sessile droplet technique was used to study the receding dynamics of oil droplets from flat hydrophilic substrates in brines of different salt type (NaCl and CaCl2) and concentration, and were studied at both low and elevated temperatures (60 and 140 °C) and pressures (1, 10, 100 and 200 bar). FINDINGS: At 1 bar and 60 °C, the minimum oil droplet-substrate adhesion force (FA) was determined at 34 mM NaCl and 225 mM CaCl2. For NaCl this strongly correlated to strengthening hydration forces, which for CaCl2 were diminished by long-range hydrophobic forces. These results highlight the importance of other non-DLVO forces governing the dewetting dynamics of heavy crude oil droplets. At 140 °C and 200 bar, the optimal brine concentrations were found to be much higher (1027 mM NaCl and 541 mM CaCl2), with higher concentrations likely attributed to weakening hydration forces at elevated temperatures.

Emerging Emulsifiers: Conceptual Basis for the Identification and Rational Design of Peptides with Surface Activity.

Emulsifiers are gradually evolving from synthetic molecules of petrochemical origin to biomolecules mainly due to health and environmental concerns. Peptides represent a type of biomolecules whose molecular structure is composed of a sequence of amino acids that can be easily tailored to have specific properties. However, the lack of knowledge about emulsifier behavior, structure-performance relationships, and the implementation of different design routes have limited the application of these peptides. Some computational and experimental approaches have tried to close this knowledge gap, but restrictions in understanding the fundamental phenomena and the limited property data availability have made the performance prediction for emulsifier peptides an area of intensive research. This study provides the concepts necessary to understand the emulsifying behavior of peptides. Additionally, a straightforward description is given of how the molecular structure and conditions of the system directly impact the peptides' ability to stabilize emulsion droplets. Moreover, the routes to design and discover novel peptides with interfacial and emulsifying activity are also discussed, along with the strategies to address some of their major pitfalls and challenges. Finally, this contribution reviews methodologies to build and use data sets containing standard properties of emulsifying peptides by looking at successful applications in different fields.

A Multi-Scale Approach to Microencapsulation by Interfacial Polymerization.

This work applies a multi-scale approach to the microencapsulation by interfacial polymerization. Such microencapsulation is used to produce fertilizers, pesticides and drugs. In this study, variations at three different scales (molecular, microscopic and macroscopic) of product design (i.e., product variables, process variables and properties) are considered simultaneously. We quantify the effect of the formulation, composition and pH change on the microcapsules' properties. Additionally, the method of measuring the strength of the microcapsules by crushing a sample of microcapsules' suspension was tested. Results show that the xylene release rate in the microcapsules decreases when the amine functionality is greater due to a stronger crosslinking. Such degree of crosslinking increases the compression force over the microcapsules and improves their appearance. When high levels of amine concentration are used, the initial pH values in the reaction are also high which leads to agglomeration. This study provides a possible explanation to the aggregation based on the kinetic and thermodynamic controls in reactions and shows that the pH measurements account for the polyurea reaction and carbamate formation, which is a reason why this is not a suitable method to study kinetics of polymerization. Finally, the method used to measure the compressive strength of the microcapsules detected differences in formulations and composition with low sensibility.

Deviation from Equilibrium Thermodynamics of an Asphaltene Model Compound during Compression-Expansion Experiments at Fluid-Fluid Interfaces.

Asphaltenes play a crucial role in crude oil behavior, and model compounds are often used to capture, mimic, and predict certain interfacial properties. In previous works, sorption of an asphaltene model compound (C5PeC11) was studied using surface pressure isotherms, where a deviation from the expected thermodynamic behavior of the interface during decane-water and air-water compression experiments was observed but not explained. In this work, the interfacial behavior of C5PeC11 was assessed at the decane-water and the air-water interfaces using a multiscale approach that includes: compression-expansion experiments on rectangular and radial Langmuir troughs, dynamic interfacial stress relaxation, and fluorescence microscopy imaging. Connections between molecular and microscopic phenomena strongly suggest that the nonthermodynamic response can be explained through a dynamic effect whose origin lies in the predominance of intermolecular forces in C5PeC11 molecules over the mechanical compression force applied. When aggregation begins at the air-water interface, stable structures are formed, and the nonthermodynamic phenomenon is not observed in subsequent compressions. However, at the decane-water interface, the initial aggregation is not consolidated due to the effect of the oil phase on the free energy of the interface allowing the high reproducibility of the dynamic effect in subsequent compression cycles. These results highlight the need to probe interfacial systems at various length scales to adequately separate equilibrium thermodynamics from dynamic responses.

Novel Bionanocompounds: Outer Membrane Protein A and Lacasse Co-Immobilized on Magnetite Nanoparticles for Produced Water Treatment.

The oil and gas industry generates large amounts of oil-derived effluents such as Heavy Crude Oil (HCO) in water (W) emulsions, which pose a significant remediation and recovery challenge due to their high stability and the presence of environmentally concerning compounds. Nanomaterials emerge as a suitable alternative for the recovery of such effluents, as they can separate them under mild conditions. Additionally, different biomolecules with bioremediation and interfacial capabilities have been explored to functionalize such nanomaterials to improve their performance even further. Here, we put forward the notion of combining these technologies for the simultaneous separation and treatment of O/W effluent emulsions by a novel co-immobilization approach where both OmpA (a biosurfactant) and Laccase (a remediation enzyme) were effectively immobilized on polyether amine (PEA)-modified magnetite nanoparticles (MNPs). The obtained bionanocompounds (i.e., MNP-PEA-OmpA, MNP-PEA-Laccase, and MNP-PEA-OmpA-Laccase) were successfully characterized via DLS, XRD, TEM, TGA, and FTIR. The demulsification of O/W emulsions was achieved by MNP-PEA-OmpA and MNP-PEA-OmpA-Laccase at 5000 ppm. This effect was further improved by applying an external magnetic field to approach HCO removal efficiencies of 81% and 88%, respectively. The degradation efficiencies with these two bionanocompounds reached levels of between 5% and 50% for the present compounds. Taken together, our results indicate that the developed nanoplatform holds significant promise for the efficient treatment of emulsified effluents from the oil and gas industry.

Probing Interfacial Structure and Dynamics of Model and Natural Asphaltenes at Fluid-Fluid Interfaces.

Asphaltenes are largely responsible for crude oil interfacial behavior. Due to their complex molecular nature, studying connections between interfacial properties and molecular structure is challenging, and these connections remain unclear. Several groups have reported on the interfacial behavior of asphaltenes, but a unified picture of both interfacial dynamics and thermodynamics is still missing. We seek to establish connections between asphaltene interfacial morphology and interfacial dynamics by combining interfacial dilatational deformation with microscopic structural imaging analysis. Understanding the behavior of natural asphaltene samples is made difficult by the inherent molecular variability. Therefore, we have also studied the behavior of an asphaltene model compound to draw fundamental structure-property relationships. This work contains simultaneous interfacial deformation and microscopy in systems of natural and model asphaltenes at air-water and decane-water interfaces. How the dynamics of natural asphaltenes influences the morphological and thermodynamic state of the air-water and decane-water interfaces is discussed based on the deviations observed between isotropic and anisotropic deformations. Areas where model asphaltenes can help us to understand the behavior of natural asphaltenes are identified such as its high surface pressure activity and aggregation character. An aggregation mechanism for model and natural asphaltenes is proposed based on an observed relationship between microscopic and millimetric aggregates.

Formulation and Characterization of Gelatin-Based Hydrogels for the Encapsulation of Kluyveromyces lactis-Applications in Packed-Bed Reactors and Probiotics Delivery in Humans.

One of the main issues when orally administering microorganism-based probiotics is the significant loss of bioactivity as they pass through the gastrointestinal (GI) tract. To overcome these issues, here, we propose to encapsulate the probiotic yeast Kluyveromyces lactis on chemically crosslinked gelatin hydrogels as a means to protect the bioactive agents in different environments. Hydrogels were prepared by the chemical crosslinking of gelatin, which is commercially available and inexpensive. This is crucial to ensure scalability and cost-effectiveness. To explore changes in key physicochemical parameters and their impact on cell viability, we varied the concentration of the crosslinking agent (glutaraldehyde) and the gelatin. The synthesized hydrogels were characterized in terms of morphological, physical-chemical, mechanical, thermal and rheological properties. This comprehensive characterization allowed us to identify critical parameters to facilitate encapsulation and enhance cell survival. Mainly due to pore size in the range of 5-10 µm, sufficient rigidity (breaking forces of about 1 N), low brittleness and structural stability under swelling and relatively high shear conditions, we selected hydrogels with a high concentration of gelatin (7.5% (w/v)) and concentrations of the crosslinking agent of 3.0% and 5.0% (w/w) for cell encapsulation. Yeasts were encapsulated with an efficiency of about 10% and subsequently tested in bioreactor operation and GI tract simulated media, thereby leading to cell viability levels that approached 95% and 50%, respectively. After testing, the hydrogels' firmness was only reduced to half of the initial value and maintained resistance to shear even under extreme pH conditions. The mechanisms underlying the observed mechanical response will require further investigation. These encouraging results, added to the superior structural stability after the treatments, indicate that the proposed encapsulates are suitable to overcome most of the major issues of oral administration of probiotics and open the possibility to explore additional biotech applications further.

Insights into the behavior of six rationally designed peptides based on Escherichia coli's OmpA at the water-dodecane interface.

The Escherichia coli's membrane protein OmpA has been identified as a potential biosurfactant due to their amphiphilic nature, and their capacity to stabilize emulsions of dodecane in water. In this study, the influence of surfactant type, concentration, preservation time and droplet size on the crystallization of n-dodecane and water, in oil-in-water emulsions stabilized with six rationally designed Escherichia coli's OmpA-based peptides was investigated. A differential scanning calorimetry (DSC) protocol was established using emulsions stabilized with Tween 20® and Tween 80®. A relationship between the surfactant concentration and the crystallization temperatures of n-dodecane and water was observed, where the crystallization temperatures seem to be dependent on the preservation time. A deconvolution analysis shows that the peak morphology possibly depends on the interactions at the interface because the enthalpic contributions of each Gaussian peak remained similar in emulsions stabilized with the same peptide. Adsorption results show that the main driver for adsorption and thus stabilization of emulsions is polar interactions (e.g. H-bonding) through the hydrophilic parts of the peptides. Those peptides with a preponderance of polar interaction groups distribution (i.e. NH2, COOH, imidazole) showed the highest interfacial activity under favorable pH conditions. This suggests that custom-made peptides whose hydrophilic/hydrophobic regions can be fine-tuned depending on the application can be easily produced with the additional advantage of their biodegradable nature.

Mechanisms of Physical Stabilization of Concentrated Water-In-Oil Emulsions Probed by Pulse Field Gradient Nuclear Magnetic Resonance and Rheology through a Multiscale Approach.

The long-term physical stability of surfactant-stabilized (Span 80 and Tween 20) concentrated water-in-mineral oil (W/O) emulsions in the presence of an electrolyte (NaCl) was studied. Pulse field gradient NMR and rheology (bulk and interfacial) were used to probe the response at the macroscopic, microscopic, and molecular levels, rendering a multiscale approach. The results show that: (1) Emulsions prepared with NaCl exhibit higher values of the elastic shear modulus ( Gwith NaCl' > Gwithout NaCl') even after ∼20 days. (2) The stabilization effect of salt against the coarsening of droplets is not due to the differences in droplet size (and thus G') or the energy incorporated through emulsification. (3) NaCl relaxes the liquid-liquid interface via a salting-in effect, which results in a lower interfacial shear elasticity ( Gwith NaCls' < Gwithout NaCls') and a higher resistance to coarsening events because of the changes in the adsorption density of the layer.

Microcalorimetry Study of the Adsorption of Asphaltenes and Asphaltene Model Compounds at the Liquid-Solid Surface.

The adsorption of an acidic polyaromatic asphaltene model compound (C5PeC11) and indigenous C6-asphaltenes onto the liquid-solid surface is studied. Model compound C5PeC11 exhibits a similar type of adsorption with a plateau adsorbed amount as C6-asphaltenes onto three surfaces (silica, calcite, and stainless steel). Model compound BisAC11, with aliphatic end groups and no acidic functionality, does not adsorb at the liquid-silica surface, indicating the importance of polar interactions on adsorption. The values of the adsorption enthalpy characterized by the ΔHz parameter (the enthalpy at zero coverage) indicate that the type of adsorption and the driving force depend on the surface, a key feature when discussing asphaltene deposition. The adsorption of C5PeC11 onto silica is shown to be driven primarily by H bonding (ΔHz = -34.9 kJ/mol), unlike adsorption onto calcite where polar van der Waals and acidic/basic interactions are thought to be predominant (ΔHz = -23.5 kJ/mol). Interactions between C5PeC11 and stainless steel are found to be weak (ΔHz = -7.7 kJ/mol). Comparing C6-asphaltenes and their esterified counterpart shows that adsorption at the liquid-solid surface is not influenced by the formation of H bonds. This was evidenced by the similar adsorbed amounts obtained. Finally, C5PeC11 captures, to a certain extent, the adsorption interactions of asphaltenes present at the calcite-oil and stainless steel-oil surfaces.

Sorption and Interfacial Rheology Study of Model Asphaltene Compounds.

The sorption and rheological properties of an acidic polyaromatic compound (C5PeC11), which can be used to further our understanding of the behavior of asphaltenes, are determined experimentally. The results show that C5PeC11 exhibits the type of pH-dependent surface activity and interfacial shear rheology observed in C6-asphaltenes with a decrease in the interfacial tension concomitant with the elastic modulus when the pH increases. Surface pressure-area (Π-A) isotherms show evidence of aggregation behavior and π-π stacking at both the air/water and oil/water interfaces. Similarly, interactions between adsorbed C5PeC11 compounds are evidenced through desorption experiments at the oil/water interface. Contrary to indigenous asphaltenes, adsorption is reversible, but desorption is slower than for noninteracting species. The reversibility enables us to create layers reproducibly, whereas the presence of interactions between the compounds enables us to mimic the key aspects of interfacial activity in asphaltenes. Shear and dilatational rheology show that C5PeC11 forms a predominantly elastic film both at the liquid/air and the liquid/liquid interfaces. Furthermore, a soft glassy rheology model (SGR) fits the data obtained at the liquid/liquid interface. However, it is shown that the effective noise temperature determined from the SGR model for C5PeC11 is higher than for indigenous asphaltenes measured under similar conditions. Finally, from a colloidal and rheological standpoint, the results highlight the importance of adequately addressing the distinction between the material functions and true elasticity extracted from a shear measurement and the apparent elasticity measured in dilatational-pendant drop setups.