Brian A. Grimes

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.

Analysis of dynamic surfactant mass transfer and its relationship to the transient stabilization of coalescing liquid–liquid dispersions

In this work, experiments describing the behavior of the separation of a model liquid-liquid dispersion with various concentrations of a synthetic surfactant are presented which indicate that there is a dynamic stabilization of initially unstable emulsions that occurs when the initial surfactant concentration approaches the concentration that provides stable emulsions. A simple model is presented to suggest the mechanism for the dynamic stabilization of these emulsion systems that considers the redistribution of surfactant into the continuous phase after a coalescence event at the emulsion-bulk dispersed phase interface and the dynamic mass transport of surfactant in the continuous phase of the emulsion. The results indicate that coalescence at the interface between the emulsion layer and the bulk dispersed phase creates a local region in the vicinity of this interface where the concentration of the surfactant is much higher than the bulk surfactant concentration which could lead to a locally, dynamically stabilized emulsion at this interface. The extent to which the local excess surfactant concentration reduces the coalescence rate depends strongly on the rate of coalescence at the dense packed layer-bulk dispersed phase interface relative to the rate of surfactant diffusion through the dense packed layer and, of course, on the surfactant adsorption constant, the maximum adsorbed surfactant concentration, and the surface to volume ratio of the dispersed phase. Furthermore, the results indicate that coalescence can also act to significantly increase the local concentration of an initially very dilute surfactant in the vicinity of the interface between the emulsion layer and the bulk dispersed phase interface.

Population Balance Model for Batch Gravity Separation of Crude Oil and Water Emulsions. Part I: Model Formulation

A population balance model for the separation of emulsions in a batch gravity settler is presented. Within the context of the model development, possible methodologies were elucidated for incorporating a) the physical properties of the bulk liquids, b) the physical properties of the phase interface, and c) the presence and functioning of interfacially active compounds. The model presented explicitly accounts for interfacial coalescence and the deformation of the emulsion zone due to the dynamic growth of the resolved dispersed phase; interfacial coalescence is modeled in terms of physically meaningful film drainage models and an approach for incorporating the accumulated buoyancy force in the dense packed layer is also discussed. Hydrodynamically hindered sedimentation is also considered in the model. The model is well suited to predict experimental batch settling data, especially data obtained from low-frequency NMR measurements of emulsion destabilization. The model predicts the evolution of the volume fraction of the dispersed phase at any axial position and time in the separator. Furthermore, the model predicts the location of the resolved dispersed phase interface as a function of time. Additionally, for any axial position and time in the settler, the model predicts the evolution of the average number density of droplets, the average volume/radius of droplets, the standard deviation of the droplet volume/radius, and the rate of growth of the droplets. The model is compared directly with experimental data for crude oil separations in Part II of this article.

Ab Initio Molecular Dynamics Study on the Interactions between Carboxylate Ions and Metal Ions in Water.

The interaction between a carboxylate anion (deprotonated propanoic acid) and the divalent Mg(2+), Ca(2+), Sr(2+), Ba(2+) metal ions is studied via ab initio molecular dynamics. The main focus of the study is the selectivity of the carboxylate-metal ion interaction in aqueous solution. The interaction is modeled by explicitly accounting for the solvent molecules on a DFT level. The hydration energies of the metal ions along with their diffusion and mobility coefficients are determined and a trend correlated with their ionic radius is found. Subsequently, a series of 16 constrained molecular dynamics simulations for every ion is performed, and the interaction free energy is obtained from thermodynamic integration of the forces between the metal ion and the carboxylate ion. The results indicate that the magnesium ion interacts most strongly with the carboxylate, followed by calcium, strontium, and barium. Because the interaction free energy is not enough to explain the selectivity of the reaction observed experimentally, more detailed analysis is performed on the simulation trajectories to understand the steric changes in the reaction complex during dissociation. The solvent dynamics appear to play an important role during the dissociation of the complex and also in the observed selectivity behavior of the divalent ions.

Density Functional Theory Study on the Interactions of Metal Ions with Long Chain Deprotonated Carboxylic Acids.

In this work, interactions between carboxylate ions and calcium or sodium ions are investigated via density functional theory (DFT). Despite the ubiquitous presence of these interactions in natural and industrial chemical processes, few DFT studies on these systems exist in the literature. Special focus has been placed on determining the influence of the multibody interactions (with up to 4 carboxylates and one metal ion) on an effective pair-interaction potential, such as those used in molecular mechanics (MM). Specifically, DFT calculations are employed to quantify an effective pair-potential that implicitly includes multibody interactions to construct potential energy curves for carboxylate-metal ion pairs. The DFT calculated potential curves are compared to a widely used molecular mechanics force field (OPLS-AA). The calculations indicate that multibody effects do influence the energetic behavior of these ionic pairs and the extent of this influence is determined by a balance between (a) charge transfer from the carboxylate to the metal ions which stabilizes the complex and (b) repulsion between carboxylates, which destabilizes the complex. Additionally, the potential curves of the complexes with 1 and 2 carboxylates and one counterion have been examined to higher separation distance (20 Å) by the use of relaxed scan optimization and constrained density functional theory (CDFT). The results from the relaxed scan optimization indicate that near the equilibrium distance, the charge transfer between the metal ion and the deprotonated carboxylic acid group is significant and leads to non-negligible differences between the DFT and MM potential curves, especially for calcium. However, at longer separation distances the MM calculated interaction potential functions converge to those calculated with CDFT, effectively indicating the approximate domain of the separation distance coordinate where charge transfer between the ions is occurring.

Potentiometric Titrations of Five Synthetic Tetraacids as Models for Indigenous C80 Tetraacids

The acid/base properties, critical micelle concentrations (cmcs), and pH-dependent solubility of five synthetic tetraacids have been studied at several ionic strengths (20-600 mM NaCl) and in the pH range of 1.5-11 using high precision potentiometric titrations, tensiometer measurements, and UV spectroscopy, respectively. The molecular weight of the tetraacids ranged between 478 and 983 g/mol. The potentiometric titration data was evaluated in terms of thermodynamic equilibrium models, developed in the light of relevant solubility data, Langmuir monolayer compressions and cmc of the different tetraacids. The results indicate that for two of the tetraacids, called BP5 and BP7, two chemical forms fully dominate the speciation of the monomers; the insoluble fully protonated form, and the soluble fully deprotonated form. The partly protonated species, only play a very minor role in the speciation of these tetraacids. For the other tetraacids the results are more complicated; for the smallest tetraacid, called BP1, all species seem to play important roles, and for the most hydrophobic, BP10, the formation of micelles and aggregates severely complicates the evaluation of the speciation. For the tetraacid BP3 one of the partly deprotonated forms seems to be important, thus confirming the structure to properties relationship. In spite of the complicated micelle formation chemistry, and although not actually measured, the acid/base properties for the monomers of BP10 were interpreted by means of surface charge densities of the micellar aggregates. The modeling indicates an increase of the aggregation number of the micelle upon acidification, a result of formation of mixed micelles incorporating the fully protonated and deprotonated species. An intrinsic pK(a) of 5.4 for BP5 was used to model the monomer pK(a) of BP10, and corresponded well with a monolayer acidity constant pK(s)(a) of 5.5 obtained from surface collapse pressures of Langmuir monolayers as a function of pH.

Population Balance Model for Batch Gravity Separation of Crude Oil and Water Emulsions. Part II: Comparison to Experimental Crude Oil Separation Data

The mathematical model presented in Part I of this article is compared to experimental data obtained from low-field NMR experiments on a heavy crude oil undergoing gravity separation with two different concentrations of a chemical demulsifier. Experimentally measured parameters are used in the model and include a) the water cut and drop size distribution of the emulsion (obtained directly from the NMR measurements), b) the densities and viscosities of the bulk liquids, and c) the interfacial tension; the results obtained from the model were used to analyze the experimental data in terms of these parameters. The model was formulated based on first-principle physical mechanisms, and thus, not only are the fitting parameters are kept to a minimum, good agreement between experiment and simulation results were obtained. The model reasonably predicts both sets of data for the different demulsifier concentrations with no change to the so-called fitting constants, but by the parameter that represents the magnitude of the interfacial force in the film drainage equations. Such a change in this physical parameter can be reasonably inferred by the action of the increased demulsifier concentration. Both the model and experimental NMR data indicate that the degree of poly-dispersity is a key factor in the rate of coalescence and subsequent rate of separation by sedimentation. This analysis illustrates the link between poly-dispersity and the coupling of coalescence and sedimentation rates; this is crucial for determining how different droplet size fractions will affect the overall efficiency of the separation and how physical properties of the fluids and phase interface can amplify or negate these phenomena. The separation model is a very helpful complement to the NMR technique as the model can output direct comparisons to the NMR data.

Selective Charging Behavior in an Ionic Mixture Electrolyte-Supercapacitor System for Higher Energy and Power

Ion-ion interactions in supercapacitor (SC) electrolytes are considered to have significant influence over the charging process and therefore the overall performance of the SC system. Current strategies used to weaken ionic interactions can enhance the power of SCs, but consequently, the energy density will decrease due to the increased distance between adjacent electrolyte ions at the electrode surface. Herein, we report on the simultaneous enhancement of the power and energy densities of a SC using an ionic mixture electrolyte with different types of ionic interactions. Two types of cations with stronger ionic interactions can be packed in a denser arrangement in mesopores to increase the capacitance, whereas only cations with weaker ionic interactions are allowed to enter micropores without sacrificing the power density. This unique selective charging behavior in different confined porous structure was investigated by solid-state nuclear magnetic resonance experiments and further confirmed theoretically by both density functional theory and molecular dynamics simulations. Our results offer a distinct insight into pairing ionic mixture electrolytes with materials with confined porous characteristics and further propose that it is possible to control the charging process resulting in comprehensive enhancements in SC performance.

Coalescence kinetics in surfactant stabilized emulsions: evolution equations from direct numerical simulations.

Lattice Boltzmann simulations were used to study the coalescence kinetics in emulsions with amphiphilic surfactant, under neutrally buoyant conditions, and with a significant kinematic viscosity contrast between the phases (emulating water in oil emulsions). The 3D simulation domain was large enough (256(3) ~ 10(7) grid points) to obtain good statistics with droplet numbers ranging from a few thousand at early times to a few hundred near equilibrium. Increased surfactant contents slowed down the coalescence rate between droplets due to the Gibbs-Marangoni effect, and the coalescence was driven by a quasi-turbulent velocity field. The kinetic energy decayed at a relatively slow rate at early times, due to conversion of interfacial energy to kinetic energy in the flow during coalescence. Phenomenological, coupled differential equations for the mean droplet diameter D(t) and the number density n(d)(t) were obtained from the simulation data and from film draining theories. Local (in time) power law exponents for the growth of the mean diameter (and for the concomitant decrease of n(d)) were established in terms of the instantaneous values of the kinetic energy, coalescence probability, Gibbs elasticity, and interfacial area. The model studies indicated that true power laws for the growth of the droplet size and decrease of the number of droplets with time may not be justified, since the exponents derived using the phenomenological model were time dependent. In contrast to earlier simulation results for symmetric blends with surfactant, we found no evidence for stretched logarithmic scaling of the form D ~ [ln (ct)](α) for the morphology length, or exponential scalings associated with arrested growth, on the basis of the phenomenological model.

Formation of Vesicles and Micelles in Aqueous Systems of Tetrameric Acids as Determined by Dynamic Light Scattering

A comprehensive dynamic light scattering (DLS) study on the system BP10Na4/water is presented. BP 10Na4 is a tetrameric fatty acid in sodium form. In order to change molecular packing conditions both electrolyte (NaCl) and alcohol (1-butanol, 1-pentanol) are added to the surfactant system. Phase diagrams of the systems reveal not only an extensive micellization, but also the occurrence of a lamellar liquid crystalline D phase. The DLS study shows an existence of vesicles at very dilute BP10Na4 concentrations ( ≪cmc) and also a co-existence of micelles and vesicles at higher BP10Na4 concentrations. Cryo-TEM pictures verify the existence of the vesicles. Based on the DLS and SLS experiments the weight-average molar mass of the micelles are estimated to be 13500 g/mol at 100 mM NaCl and 22700 g/mol at 600 mM. The corresponding aggregation numbers are 13 and 22, respectively.