A hydrophobic associating polymer named DiPHAM (acrylamide/sodium acrylamide-2-methylpropanesulfonic/sodium acrylate/N,N-di-n-dodecylacrylamide) with good salt tolerance was synthesized via photo-initiation polymerization. The critical association concentration (CAC) of DiPHAM was determined by viscosity changes to be 490 mg/L with different DiPHAM concentrations and particle sizes varied under such dynamic conditions. The influences of aqueous metal ions with different charges on its aqueous solution were investigated by measuring apparent viscosity, viscoelasticity, thixotropy, rheology, and particle size, and by SEM observation. The apparent viscosity of the DiPHAM solution was affected by metal ions to some extent, but the viscosity of the polymer can be still maintained at 55 mPa·s under 20 × 104 mg/L NaCl. Divalent metal ions show greater impact on DiPHAM aqueous solutions, but the polymer solutions showed resistance to the changes caused in viscosity, structure, and viscoelasticity by Ca2+ and Mg2+ ions. The salt tolerance of DiPHAM is due to the combination of hydrophobic association, the electrostatic shield, and double layer compression of the hydration shell. Increasing the ion concentration enhances the dehydration and further compresses the hydration shell, making the non-structural viscosity decrease, even “salting out”. Measurements of rheological properties showed that DiPHAM solutions could maintain a relatively high viscosity (0.6%-71 mPa·s/0.3%-50 mPa·s) after 120 min of continuous shearing (170 s−1) at 140 °C. Under high-salinity (5000 mg/L Ca2+/3000 mg/L Mg2+) conditions, the solution with 0.6 wt% DiPHAM still maintained a high viscosity (50 mPa·s/70 mPa·s) after continuously shearing for 120 min at 120 °C and 170 s−1. The good salt tolerance of DiPHAM can lead to a variety of applications, including in fracturing fluids for enhanced oil recovery (EOR) and in sewage treatment.
In order to improve the heat resistance of current clean fracturing fluids, a novel cationic surfactant (VES-T), composed of three single-chains and a spacer group, was designed and synthesized as thickener for the fluids. Various performances of such VES-T fluid in the presence of NaSal were evaluated carefully. Study of the rheological properties demonstrated that the fluids with varying concentrations (3–5 wt %) of VES-T have excellent thermal stabilities under ultra-high temperatures ranging from 140 to 180 °C. Until now, this is the highest temperature that the VES fracturing fluid could bear. The VES-T/NaSal fluid exhibited good viscoelasticity and proppant-suspending capability, which was attributed to the three-dimensional network formed by entangled wormlike micelles. Furthermore, the VES fracturing fluids can be completely gel broken by standard brines within 2 h. Thus, the VES-T synthesized in this work has a good prospect for utilization during the development of ultra-high temperature reservoirs.
Gemini surfactant, as a functionally flexible polymer-like material in the aqueous solution, has attracted increased attention in reservoir stimulation of hydraulic fracturing in recent decades. A new Gemini cationic viscoelastic surfactant named JS-N-JS, which has a secondary amine spacer group and two ultra-long hydrophobic tails, was synthesized from erucamidopropyl dimethylamine, diethanolamine, and thionyl chloride as a thickener for hydraulic fracturing fluid. Compared with some Gemini cationic surfactant with methylene spacer, JS-N-JS showed a lower critical micellar concentration (CMC) and higher surface activity due to the hydrogen bond formed between the secondary amine and water molecule intends to reduce electrostatic repulsion, which is more beneficial to be the fracturing fluid thickener. Moreover, the performance of JS-N-JS solution can be further improved by salts of potassium chloride (KCl) or sodium salicylate (NaSal), while organic salt behaved better according to the measurements. The SEM observation confirmed that JS-N-JS/NaSal system owned a tighter network microstructure, and JS-N-JS/NaSal system exhibited a distinct superior viscoelasticity system at a sweep frequency of 0.1–10 Hz. As a fracturing fluid, the solution with a formula of 30 mmol JS-N-JS and 100 mmol NaSal was evaluated according to the petroleum industrial standard and presented excellent viscoelastic properties, the viscosity of which can maintain above 70 mPa·s for 110 min under a shear rate of 170 s−1 at 120 °C. Meanwhile, the drag reducing rate of the formula could reach above 70% with the increase of shear rate. Finally, the viscous fracturing fluid can be broken into the water-like fluid in 1.2 h after being fully exposed to hydrocarbons and the water-like fluid presented a low damage to the tight sand reservoirs according to the core flooding experiments, in which the permeability recovery rate can reach 85.05%. These results fully demonstrate that the JS-N-JS solution fully meets the requirement of the industrial application of hydraulic fracturing.
The quaternary polymer was synthesized by radical polymerization and characterized by 1H NMR. The tests of critical associating concentration and SEM suggest that there is a multilayered and robust network structure in the polymer solution. An excellent elasticity in the polymer solution by the first normal stress difference, viscoelasticity, and thixotropy was observed. The critical crosslinker concentration of polymer with sodium dodecyl sulfate and its interaction mechanism were investigated. According to the reaction kinetics, the supramolecular structure had the lowest activation energy, stable network structure, and greater thermal stability. Then the polymer was employed in the fracturing fluid due to its excellent elasticity using the intermolecular forces, which showed superior sand suspension capacity by dynamic sand suspension measurement. Meanwhile, a theoretical analysis was proposed as to why polymer solution has excellent suspension and drag reduction properties. Therefore, this polymer could be an alternative in many fields, especially in fracking, which is significant for the development of oil and gas resources in deep wells.