Dynamic Asphaltene-Stearic Acid Competition at the Oil-Water Interface.

Interfacial tension (IFT) is one of the major parameters which govern the fluid flow in oil production and recovery. This paper investigates the interfacial activity of different natural surfactants found in crude oil. The main objective was to better understand the competition between carboxylic acids and asphaltenes on toluene/water interfaces. Dynamic IFT was measured for water-in-oil pendant drops contrary to most studies using oil-in-water drops. Stearic acid (SA) was used as model compound for surface-active carboxylic acids in crude. The influence of concentration of these species on dynamic IFT between model oil and deionized water was examined. The acid concentrations were of realistic values (total acid number 0.1 to 2 mg KOH/g oil) while asphaltene concentrations were low and set between 10 and 100 ppm. In mixtures, the initial surface pressure was entirely determined by the SA content while asphaltenes showed a slow initial diffusion to the interface followed by increased adsorption at longer times. The final surface pressure was higher for asphaltenes compared to SA, but for binaries, the final surface pressure was always lower than the sum of the individuals. At high SA concentration, surface pressures of mixtures were dominated entirely by the SA, although, Langmuir isotherm analysis shows that asphaltenes bind to the interface 200-250 times stronger than SA. The surface area/molecule for both SA and asphaltenes were found to be larger than the values reported in recent literature. Various approaches to dynamic surface adsorption were tested, showing that apparent diffusivity of asphaltenes is very low, in agreement with other works. Hence, the adsorption is apparently under barrier control. A possible hypothesis is that at the initial phase of the experiment and at lower concentration of asphaltenes, the interface is occupied by stearic acid molecules forming a dense layer of hydrocarbon chains that may repel the asphaltenes.

Quantifying mineral surface energy by scanning force microscopy.

Fundamental understanding of the wettability of carbonate formations can potentially be applied to the development of oil recovery strategies in a complex carbonate reservoir. In the present study, surface energies of representative carbonate samples were evaluated by direct quantitative force measurements, using scanning force microscopy (SFM) at sub-micron scale, to develop a reliable method to predict reservoir wettability. Local adhesion force measurements were conducted on appropriate calcite and dolomite samples and performed in air as well as in the presence of polar and nonpolar fluids. This study demonstrated that, by comparing measurements of adhesion forces between samples of the same mineral in different fluids, it is feasible to determine the surface energy of a given mineral as well as its polar and nonpolar components. The derived values are in agreement with literature. A proof-of-principle protocol has been established to quantify surface energy using SFM-based adhesion measurements. This novel methodology complements the conventional contact angle measurement technique, where surface energy can only be examined at large length scale. The reported methodology has great potential for further optimization into a new standard method for fast and accurate surface energy determination, and hence provides a new tool for reservoir rock wettability characterization.

Spontaneous imbibition in nanopores of different roughness and wettability.

The spontaneous imbibition of liquid in nanopores of different roughness is investigated using coarse grain molecular dynamics (MD) simulation. The numerical model is presented and the simplifying assumptions are discussed in detail. The molecular-kinetic theory introduced by Blake is used to describe the effect of dynamic contact angle on fluid imbibition. The capillary roughness is modeled using a random distribution of coarse grained particles forming the wall. The Lucas-Washburn equation is used as a reference for analyzing the imbibition curves obtained by simulation. Due to the statistical nature of MD processing, a comprehensive approach was made to average and smooth the data to accurately define a contact angle. The results are discussed in terms of effective hydrodynamic and static capillary radii and their difference as a function of roughness and wettability.

Osmotic pressure acting on a semipermeable shell immersed in a solution of polyions.

We study theoretically the osmotic equilibria for a shell immersed in a suspension of polyions (e.g., colloids, polyelectrolytes, etc.). The shell is treated as impermeable for polyions, but allowing free diffusion of counterions that permeate inside the shell. From the solution of linearized Poisson-Boltzmann equation, we obtain the distribution of a potential and concentration profiles for polyions and counterions. We then obtain an explicit formula for the excess osmotic pressure of a polyion solution exerted on the shell, which includes a quadratic term in order to provide a self-consistency of a linear theory. As a result this pressure is larger than given by a concentration of polyions at the outer shell boundary obtained within linearized theory. It is, however, always smaller than or equal to the bulk osmotic pressure. This difference is attributed to a repulsive electrostatic disjoining pressure due to an overlap of counterion clouds inside the shell. A comparison with molecular dynamics simulations is provided and demonstrates that although the concentration profiles obtained within a linear theory deviate from simulation data at large potential, the theoretical and simulation pressures are in surprisingly good harmony.

Flow of wormlike micelles in an expansion-contraction geometry.

Recently there has been a great deal of attention, from researchers both in academia and in industry, focused on the rheological properties of solutions of viscoelastic wormlike micelles formed by surfactants. It is particularly vital to understand the properties of these solutions with regard to their flow in porous media, given their application to the recovery of hydrocarbons from subterranean formations. In this study a realistic mesoscopic Brownian dynamics model has been utilized to investigate the flow of viscoelastic surfactant (VES) fluid through individual pores with sizes of around one micron. In particular the influence of micelle size, pore geometry and flow rate on the ability of worms to pass through the pores was studied. The ways in which these parameters influence the conformational properties of the worms and the spatial distribution of micelles inside the simulation cell was also investigated. Despite the observation that the density and length distributions became non-uniform at higher scission energy, the distribution of breaking and fusion events remained spatially uniform.

Stability of toroid and rodlike globular structures of a single stiff-chain macromolecule for different bending potentials.

We study the effect of the bending potential on the stability of toroidal and rodlike globules which are typical collapsed conformations of a single stiff-chain macromolecule. We perform numerical calculations in the framework of the bead-stick model of a polymer chain. The intrinsic structure of globules is also analyzed. It was shown that the bending potential affects the packing geometry of bundles in a toroidal globule in the ground state. This potential also influences the bends at the ends of a rodlike globule: both the shape of the loops and the number of bonds in each loop have been investigated numerically as well as by Monte Carlo computer simulations performed for a separate loop. Our main results are (1) the shape of the bending potential could be possibly seen from the geometry of a globule; (2) toroidal globules are always more favorable than the rodlike ones.

Spatial distribution of polyelectrolyte and counterions in nanocapsules: a computer simulation study.

We study a spatial distribution of polyelectrolyte chains and counterions inside nanometer-size capsules by means of molecular dynamics simulation on the level of a colloidal model in which polyelectrolyte coils are modeled as soft charged spheres. The capsule shell is treated as a semipermeable membrane, impermeable for the polyelectrolyte chains, but allowing free diffusion of solvent molecules and counterions. As a result, counterions leak out from the capsule immersed into a fluid of low ionic strength. This counterion leakage leads to a formation of characteristic polyelectrolyte density profiles with the central plateau and large peaks at the wall. We show that a nonuniform distribution of the inner polyelectrolyte depends on the capsule radius, surface charge, concentration of encapsulated polyelectrolyte, and the volume fraction of capsules.