In Situ Produced Nanoparticles at the Oil-Water Interface for Conformance Control and Enhanced Oil Recovery.

Nanoparticle-assisted enhanced oil recovery (Nano-EOR) has attracted intensive interest in the laboratory as a promising oil recovery technology. However, the nanoparticles' stability and long-distance delivery of nanoparticles (NPs) in large-scale reservoirs are two main challenges. In this work, we developed a novel concept of in situ synthesizing NPs at the oil-water interface inside the reservoir for EOR instead of injecting presynthesized NPs from outside. The pore-scale flooding experiments show that EOR efficiencies for tertiary flooding were 6.3% without reaction (Case 3), 14.6% for slow reaction (Case 1), and 25.4% for relatively quick reaction (Case 4). Examination of the EOR mechanism shows that in situ produced SiO2 NPs in microchannels could alter the substrate wettability toward neutral wetting. Moreover, the produced NPs tended to assemble on the immiscible oil-water interface, forming a barrier toward interface deformation. As the reaction continued, excessive surface-modified NPs could also diffuse into aqueous brine and accumulate as a soft gel in the flowing path swept by brine. Collectively, these processes induced a "shut-off" effect and diverted displacing fluids to unswept areas, which consequently increased the sweep efficiency and improved the oil recovery efficiency. Auxiliary bulk-scale experiments also showed that the reaction-induced nanoparticle synthesis and assembly at an immiscible interface reduced the interfacial tension and generated an elastic oil-water interface.

Kinetic Study of Controlled Asphaltene Inhibitor Release from Nanoemulsions.

Asphaltene aggregation and subsequent precipitation in the nonpolar medium may have a profound effect on plugging wellbores and production equipment. Continuing our work on controlled release of asphaltene inhibitor (AI) by using nanoemulsions (NEs), this work provides new evidence about long-term asphaltene stability by using optical measurement and reveals the kinetic processes of inhibitor transport/release mechanisms. Multiple light scattering (Turbiscan) and dynamic light scattering have been used to study "in situ" the effectiveness and performance of the proposed controlled release in three cases of asphaltene aggregation/precipitation in the presence of: (i) strong organic acids (dodecyl benzene sulfonic acid, DBSA), (ii) NEs (blank NEs), and (iii) NEs loaded with DBSA (DBSA NEs). The results suggested that the new approach reduced the amount of AI by ∼20 times and achieved high asphaltene inhibition efficiency of ∼84% with a prolonged release time. A mechanistic understanding of the controlled release effect was proposed based on the effect of DBSA NEs on the asphaltene particle morphology variation, which was related to the hydrophilicity of DBSA and the strong intermolecular interactions among all DBSA NE components. The release mechanism of the AI from the NE was evaluated using eight release models and was found to follow the Korsmeyer-Peppas kinetic model.

Molecular structure characterization of asphaltene in the presence of inhibitors with nanoemulsions.

Molecular structure characteristics and morphological features of asphaltene can be significantly influenced by the addition of asphaltene inhibitors (AI). We have recently developed a novel concept of using nanoemulsions (NE) as carriers for controlled release of asphaltene inhibitors, which could prohibit the precipitation problem with reduced AI quantity. In this work, X-ray diffraction (XRD) was utilized to investigate the changes in the stacking behaviour of asphaltenes in the presence of three cases: (i) strong organic acids (dodecyl benzene sulfonic acid, DBSA), (ii) nanoemulsions (blank NEs), and (iii) nanoemulsion loaded DBSA (DBSA NEs). Based on the XRD and transmission electron microscopy (TEM) analyses, the stacking distance between aromatic rings of asphaltene was found to be increased by 22.2%, suggesting that the modification of the π system over the aromatic zone prevented the ultimate π-π interactions between asphaltene sheets. The evidence of multiple intermolecular interactions quantitatively obtained from Fourier-transform infrared spectroscopy (FTIR) supported our proposed mechanism for controlled release effect and long-term asphaltene stability, i.e., the decrease of the aromaticity and the reduction in the aliphatic side chains of asphaltene. The refractory nature of asphaltenes was examined by thermogravimetric analysis (TGA), which showed that the asphaltene structure was improved considerably and the coke yield was decreased by 62% due to the decrease of the cluster size and the increase of the stacking distance.