Wax appearance temperature (WAT), defined as the temperature at which the first solid paraffin crystal appears in a crude oil, is one of the key flow assurance indicators in the oil industry. Although there are several commonly-used experimental techniques to determine WAT, none provides unambiguous molecular-level information to characterize the phase transition between the homogeneous fluid and the underlying solid phase. Molecular Dynamics (MD) simulations employing the statistical associating fluid theory (SAFT) force field are used to interrogate the incipient solidification states of models for long-chain alkanes cooled from a melt to an arrested state. We monitor the phase change of pure long chain n-alkanes: tetracosane (C24H50) and triacontane (C30H62), and an 8-component surrogate n-alkane mixture (C12-C33) built upon the compositional information of a waxy crude. Comparison to Diffusion Ordered Spectroscopy Nuclear Magnetic Resonance (DOSY NMR) results allows the assessment of the limitations of the coarse-grained models proposed. We show that upon approach to freezing, the heavier components restrict their motion first while the lighter ones retain their mobility and help fluidize the mixture. We further demonstrate that upon sub-cooling of long n-alkane fluids and mixtures, a discontinuity arises in the slope of the self-diffusion coefficient with decreasing temperature, which can be employed as a marker for the appearance of an arrested state commensurate with conventional WAT measurements.
In poorly consolidated carbonate rock reservoirs, solids production risk, which can lead to increased environmental waste, can be mitigated by injecting formation-strengthening chemicals. Classical atomistic molecular dynamics (MD) simulation is employed to model the interaction of polyacrylamide-based polymer additives with a calcite structure, which is the main component of carbonate formations. Amongst the possible calcite crystal planes employed as surrogates of reservoir rocks, the (1 0 4) plane is shown to be the most suitable surrogate for assessing the interactions with chemicals due to its stability and more realistic representation of carbonate structure. The molecular conformation and binding energies of pure polyacrylamide (PAM), hydrolysed polyacrylamide in neutral form (HPAM), hydrolysed polyacrylamide with 33% charge density (HPAM 33%) and sulfonated polyacrylamide with 33% charge density (SPAM 33%) are assessed to determine the adsorption characteristics onto calcite surfaces. An adsorption-free energy analysis, using an enhanced umbrella sampling method, is applied to evaluate the chemical adsorption performance. The interaction energy analysis shows that the polyacrylamide-based polymers display favourable interactions with the calcite structure. This is attributed to the electrostatic attraction between the amide and carboxyl functional groups with the calcite. Simulations confirm that HPAM33% has a lower free energy than other polymers, presumably due to the presence of the acrylate monomer in ionised form. The superior chemical adsorption performance of HPAM33% agrees with Atomic Force Microscopy experiments reported herein.
In this work, the interaction of hydrolysed polyacrylamide (HPAM) of two molecular weights (F3330, 11-13 MDa; F3530, 15-17 MDa) with calcium carbonate (CaCO3) was studied via atomic force microscopy (AFM). In the absence of polymers at 1.7 mM and 1 M NaCl, good agreement with DLVO theory was observed. At 1.7 mM NaCl, repulsive interaction during approach at approximately 20 nm and attractive adhesion of approximately 400 pN during retraction was measured, whilst, at 1 M NaCl, no repulsion during approach was found. Still, a significantly larger adhesion of approximately 1400 pN during retraction was observed. In the presence of polymers, results indicated that F3330 displayed higher average adhesion (450-625 pN) and interaction energy (43-145 aJ) with CaCO3 than F3530's average adhesion (85-88 pN) and interaction energy (8.4-11 aJ). On the other hand, F3530 exerted a longer steric repulsion distance (70-100 nm) than F3330 (30-70 nm). This was likely due to the lower molecular weight. F3330 adopted a flatter configuration on the calcite surface, creating more anchor points with the surface in the form of train segments. The adhesion and interaction energy of both HPAM with CaCO3 can be decreased by increasing the salt concentration. At 3% NaCl, the average adhesion and interaction energy of F3330 was 72-120 pN and 5.6-17 aJ, respectively, while the average adhesion and interaction energy of F3530 was 11.4-48 pN and 0.3-2.98 aJ, respectively. The reduction of adhesion and interaction energy was likely due to the screening of the COO- charged group of HPAM by salt cations, leading to a reduction of electrostatic attraction between the negatively charged HPAM and the positively charged CaCO3.
Hypothesis Atomistically-detailed models of surfactants provide quantitative information on the molecular interactions and spatial distributions at fluid interfaces. Hence, it should be possible to extract from this information, macroscopical thermophysical properties such as interfacial tension, critical micelle concentrations and the relationship between these properties and the bulk fluid surfactant concentrations. Simulations and Experiments Molecular-scale interfacial of systems containing n-dodecyl β-glucoside (APG12) are simulated using classical molecular dynamics. The bulk phases and the corresponding interfacial regions are all explicitly detailed using an all-atom force field (PCFF+). During the simulation, the behaviour of the interface is analyzed geometrically to obtain an approximated value of the critical micelle concentration (CMC) in terms of the surfactant area number density and the interfacial tension is assessed through the analysis of the forces amongst molecules. New experimental determinations are reported for the surface tension of APG12 at the water/air and at the water/n-decane interfaces. Findings We showcase the application of a thermodynamic framework that inter-relates interfacial tensions, surface densities, CMCs and bulk surfactant concentrations, which allows the in silico quantitative prediction of interfacial tension isotherms.