New Insights and Experimental Investigation of High-Temperature Gel Reinforced by Nano-SiO2.

The properties of a reinforced gel with partially hydrolyzed polyacrylamide (HPAM) as the main agent, water-soluble phenolic resin (WSPR) as the crosslinker, and nano-SiO2 as the stabilizer were evaluated in terms of gelation time, gel strength and thermal stability under the conditions of 110 °C and 12.124 g/L salinity in water. The results showed that the gelation time of the gel with high strength was adjustable from 3 to 23 h, remaining stable for more than 180 days under stratigraphic conditions, although with a certain degree of early dehydration in the gel. Cryo-scanning electron microscopy (cryo-SEM) and dynamic light scattering (DLS) analysis revealed that nano-SiO2 improves the dispersion of the polymer in water, resulting in a more homogeneous structure of the formed gel and thus improving the strength of the gels. In addition, rheological tests and cryo-SEM showed that the interaction between nano-SiO2 and the polymer could inhibit the degradation of polymer to a certain extent and improve the thermal stability of the gel. However, the oxidative degradation of the gel is still the main cause of early dehydration of water-soluble phenolic resin gel, and the addition of a small amount of hydroquinone to the gelants can significantly improve the antioxidative degradation properties of phenolic resin gel.

Syneresis Behavior of Polymer Gels Aged in Different Brines from Gelants.

Gel syneresis is a common problem in gel treatment for oil recovery applications. In this study, a stable gel was prepared in a soft brine by using a water-soluble phenolic resin as a crosslinker, nanoparticles as a stabilizer, and partially hydrolyzed polyacrylamide (HPAM) or copolymers with different contents of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) groups as polymers. The syneresis behavior of the gels formed in a soft brine was evaluated upon aging in hard brines. The results show that when the salinity of the hard brine is lower than 30,000 mg/L, the gel expands, and its strength decreases; when the salinity of the hard brine is higher than 50,000 mg/L, the gel exhibits syneresis, and its strength increases. The effects of various influencing factors on the gel syneresis behavior were also evaluated. It was found that optimizing the polymer structure and adding nanoparticles can effectively overcome gel syneresis and enhance gel stability. Based on the research described in this paper, some proposals for designing salt-resistant polymer gels are presented.

pH- and thermo-responsive Pickering emulsion stabilized by silica nanoparticles and conventional nonionic copolymer surfactants.

HYPOTHESIS: Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) could be adsorbed on the silica surface via the hydrogen bonding between PEO and silanol (SiOH) groups. This interaction would be inhibited once SiOH is dissociated to SiO- at an increased pH value. Besides, the adsorption should be affected by temperature considering the nature of hydrogen bond. Hence, we speculate that silica nanoparticles modified in situ by adsorbed PEO-PPO-PEO possess a pH- and thermo-sensitive surface activity, making them a stimuli-responsive Pickering emulsifier. EXPERIMENTS: Paraffin oil-in-water emulsions stabilized by silica nanoparticles and PEO-PPO-PEO were prepared. Stabilities, droplet morphologies and stimuli-responses were systematically studied using bottle test, optical microscopy and cryo-scanning electron microscopy (cryo-SEM). To clarify the emulsification mechanism, interfacial viscoelastic moduli and desorption energies were determined using the data obtained from drop shape analysis. FINDINGS: Silica nanoparticles are hydrophobized and flocculated by adsorbed PEO-PPO-PEO at a relatively low pH and room temperature. Upon the pH or the temperature increased, particles regain their hydrophilicity and dispersity due to the desorption of surfactants. Emulsions stabilized by these surfactant-modified particles are pH- and thermo-responsive and can be repetitively switched between stabilization and destabilization. The switch temperature is controlled by the PEO length. The emulsification mechanism is verified in view of interfacial viscoelasticity and desorption energy. These findings demonstrate a novel and simple strategy of preparing pH- and thermo-responsive Pickering emulsions desirable to many industrial applications.

Emulsion Acid Diversion Agents for Oil Wells Containing Bottom Water with High Temperature and High Salinity.

Conventional acid diversion agents cannot tolerate the high temperature and salinity of acidizing water-producing oil wells that contain bottom water and heterogeneous layers. Therefore, a water/oil (w/o) emulsion was proposed as an acid diversion agent to promote acidification. The selected emulsifier, oleic acid imidazoline, is a switchable emulsifier. Because this emulsifier reacts with acids to transform amines into ammonium, the emulsion rapidly demulsifies, and the emulsion acid diversion agent can use the spent acid flowback to remove plugging. Evaluation of the emulsion properties indicated that a 10 wt % emulsifier generated a stable emulsion at oil/water ratios from 1:9 to 4:6 at 90 °C. Viscosity was higher at lower oil/water ratios, and the emulsion with an oil/water ratio of 4:6, which had a low viscosity, was injected into the formation. During injection, the emulsion continued to emulsify in high-permeability channels, which increased the viscosity until the water layer was blocked. During experiments, single-tube and dual-tube models were designed to evaluate the injectivity and plugging selectivity of this emulsion. The results showed that the resistance factors exceeded 14 in the high-permeability cores when the emulsion was injected. The higher permeability ratio in parallel cores allowed a larger emulsion volume to enter the high-permeability cores. In experiments using parallel cores, the block rate of the high-permeability cores exceeded 92%, and that of the low-permeability cores was less than 12%. Finally, this emulsion was injected into two groups of parallel carbonate cores for acidification diversion tests. The results indicated that the permeability of the acidified low-permeability core was basically the same as that of the high-permeability core plugged by the emulsion. The findings of this study improve the understanding of the feasibility and advantages of using emulsions as acid diversion agents for high-temperature and high-salinity oil wells containing bottom water.

Effects of Extended Surfactant Structure on the Interfacial Tension and Optimal Salinity of Dilute Solutions.

Extended surfactants with the oxypropylene (PO) group and ethoxylated anionic surfactants with the oxyethylene (EO) group have a high salt tolerance capability. Most of the researches on extended surfactants and ethoxylated anionic surfactants focused on the microemulsion, solubilization, and interfacial tension (IFT) of concentrated surfactant solutions, whereas a few researches focused on the IFT of dilute surfactant solutions. Moreover, a previous work focused only on surfactants with PO numbers greater than 4 and copolymers of PO and EO. The effects of extended surfactants containing short PO chains and no EO groups have not been examined. We measured the IFT and optimal salinity between n-alkanes and dilute solutions of extended surfactants or ethoxylated sulfonates at 30 °C. The effects of the surfactant structure on the equilibrium interfacial tension (IFTeq) and optimal salinity of the system were studied in detail. As for the effects on IFT, results indicate that the introduction of PO groups leads to their enhanced capability to reduce the IFT prior to cross-salinity and a reduction in the IFT between n-alkanes and surfactant solutions to ultralow values (smaller than 0.01 mN/m) near the optimal salinity. It was also found that extended surfactants with different alkyl chains also entail a cross-salinity; at values lower than the cross-salinity, the IFT reduction capacity of extended surfactants with a long alkyl chain (C16P3SO3) is better than that of extended surfactants with a short alkyl chain (C13P3SO3). As for the effect on the optimal salinity, it was found that the optimal salinity of extended surfactants is lower than that of ethoxylated sulfonates for the same oil phase. It was also found that the optimal salinity of extended surfactants first increased and later decreased with increasing PON. This finding is first proposed based on summarizing some researchers' studies and our experiments.