Optimizing acid microemulsions for cleaner gas production: A study on enhanced adsorption characteristics and implications in retardation.

The ultralow interfacial tension between the oil and aqueous phases and the solubilization characteristics in microemulsion systems make them useful for surface cleaning and enhanced oil recovery applications. Microemulsions can form an adsorbed barrier on rock, reducing the acid-rock reaction rate. However, as acid retardation additives, the adsorption patterns of microemulsions are not clearly defined. In this study, microemulsions composed of various electrical surfactants, oil cores, and oil core additives were obtained, and their phase behaviors were investigated. Through adsorption and reaction experiments, cleaning microemulsions that enhance adsorption effects were identified, and their adsorption patterns and adaptability under flow conditions were evaluated. The results demonstrate that incorporating negatively charged polar compounds forms an enhanced adsorption microemulsion characterized by an average droplet size of less than 30 nm after mixing with the acid. The introduction of negatively charged polar compounds resulted in a 177 % increase in adsorption and an 81 % improvement in static retardation effect. Dynamic adsorption tests indicate that the pseudo-second-order model more accurately describes the kinetics of dynamic adsorption of microemulsions on rock surfaces. Under a fixed flow rate, the dynamic retardation rate increased with the concentration of the microemulsion. In practical acidification, the adsorption of microemulsions results mainly from combined electrostatic forces and fluid scouring, characterized by a continuous process of adsorption and desorption. Scanning electron microscope also confirmed that microemulsions can form an adsorptive film on the rock, reducing the acid-rock reaction rate. This study offers practical guidelines for the selection and application of retardation additives, aiming to enhance the ecological compatibility of chemical treatments in low-permeability limestone reservoirs.

Mechanism of Salt Precipitation Blockage in Low-Producing Gas Wells and the Method of Acidification Blockage Removal.

In the Changqing area, over 23.6% of gas wells produce less than 0.1 × 104 m3/d of gas daily, posing a challenge to gas field sustainability. Laboratory analysis of scale samples from three wells and formation water analysis via inductively coupled plasma revealed soluble salt as the primary well blockage, with sodium chloride and calcium chloride comprising 48.0-81.2% of total content. The G3# well blockage contains a small amount of quartz from acid-insoluble components of carbonate acidification. Formation water from all wells exhibited high salinity (up to 153 g/L) with a calcium chloride water type. Scanning electron microscopy and EDS confirmed halite and quartz features in blockage samples. Theoretical calculations show salt crystallization when tubing pressure falls below 10 MPa and daily water production is <1.0 tons/day. Lower production leads to lower tubing pressure and higher salt precipitation at the bottom of the well. For G1# and G2# blockages, HCl dissolves >90%, and water >85%, making them suitable removal agents. For 3# blockage, mud acid with >80% dissolution is recommended. Chemical methods effectively clean the wellbore and formation. Optimized blockage removal measures increase tubing pressure and daily production by 2.18 and 4.05 times, respectively. This study offers insights into addressing well blockage challenges in low-producing gas wells.

Optimization of Fracturing Fluid and Retarded Acid for Stimulating Tight Naturally Fractured Bedrock Reservoirs.

In tight naturally fractured bedrock reservoirs, hydrocarbons are typically stored in fractures, where hydraulic fracturing is needed to connect these fractures to the wellbore. The cross-linked gel is used as the fracturing fluid to reduce the fluid leak-off through natural fractures; however, it can cause formation damage due to its high content of residues after breaking. A synthetic polymer is introduced and evaluated that can maintain a high viscosity to minimize the leak-off , while having a low residue content after breaking. To further enhance the conductivity of the created fracture network, acid is applied to etch and roughen the created fracture faces. Because the target reservoir has a complex mineral composition, a three-step coreflood sequence using reservoir rock samples with controlled fracture widths is established to quantify the enhancement of different retarded acids and to reveal the mechanism behind it. The results indicate the synergy effect of reducing the acid concentration and surfactant adsorption on rock surfaces can lead to an obvious enhancement of the fracture permeability after acidizing, while the mud acid or hydrofluoric acid is not suitable for the target reservoir where concentrations of silicates and clays are relatively high.

Study on the Effect of Fracturing Fluid on the Structure and Mechanical Properties of Igneous Rock.

Igneous rock oil and gas reservoirs have great development potential. Hydraulic fracturing is an important means for the development of these reservoirs. In the process of fracturing and increasing production, fracturing fluid is prone to a hydration reaction with clay minerals in igneous rock, and then, the structure and mechanical properties of the igneous rock are changed, affecting increased production. Therefore, it is necessary to establish a systematic water-rock reaction experiment method to understand the influence of fracturing fluid on the structure and mechanical properties of igneous rocks and to optimize the fracturing fluid system of igneous rock reservoirs. In this experiment, four solutions were used: slickwater, guar fracturing fluid, 2% KCl aqueous solution, and 4% KCl aqueous solution. Acoustic testing, porosity and permeability testing, XRD analysis, micro-CT scanning, and displacement experiments were performed. The influence of different fracturing fluids on the structure and mechanical properties of igneous rocks was studied. Igneous rock samples with a permeability of 0.05-0.1 mD and average porosity of 7-14% were used. The results show that all four liquid systems will reduce the permeability, Young's modulus, and brittleness index and increase the porosity and Poisson's ratio of the rock after fracturing. Among them, the permeability damage rate is as high as 37.37%, which may be related to the plugging of pores with solid residues in the gel breaking liquid; CT results show that there are microcracks in the rock, which increase over time, up to 13.54%. The brittleness index decreases. Among the fluids, the influence of slickwater on the rock brittleness index is the smallest, no more than 5%. Guar gum had the greatest effect on the Gel breaking liquid, up to 58%. One of the reasons for the increase in porosity is that adding a clay stabilizer composed of inorganic salts and organic cationic polymers to the slickwater fracturing fluid can effectively reduce the damage caused by the fracturing fluid to the rock during the fracturing process and can reduce the maximum by 50%. This paper can clarify the damage law of fracturing fluid systems to igneous rock reservoirs and provide the theoretical basis for the hydraulic fracturing of igneous rock reservoirs.

High-Temperature-Resistant, Low-Concentration Water-Controlling Composite Cross-Linked Polyacrylamide Weak Gel System Prepared from Oilfield Sewage.

The polyacrylamide weak gel is an effective system to block a high-permeability layer, realize water control, and enhance oil recovery. However, its application is limited by poor temperature resistance and high polymer dosage. In this paper, an inorganic-organic composite cross-linking agent was synthesized by using Cr(III) and phenolic resin. The composite cross-linking agent can cross-link low concentrations of polyacrylamide to obtain a high-temperature-resistant weak gel system in oilfield sewage. By adjusting the ratio of Cr(III), phenolic resin, and polyacrylamide, an optimum formula MF-7 can be obtained according to the gel strength. Results from evaluation experiments show that the strength of MF-7 can reach H grade even at polyacrylamide concentrations as low as 0.3%. The temperature resistance of the weak gel system is up to 100 °C, and no syneresis occurs after 330 h at 95 °C. Scanning electron microscopy (SEM) results show that MF-7 has a three-dimensional network structure with spherical nodes. The spherical node is composed of polyacrylamide, and its structure size is completely matched with the hydrodynamic radius of the used polyacrylamide. When combined with the network structure formed by Cr(III), the dense cross-linking network structure with nodes can greatly improve the strength and thermal stability of the gel system. The higher the molecular weight of the polyacrylamide used, the higher the strength of the gel obtained. Overall, the composite cross-linking agent can synergistically improve the mechanical properties of the gel, and this weak gel system formed by oilfield sewage is more economical and tolerant.

Performance Evaluation of the Multifunctional Variable-Viscosity Slick Water for Fracturing in Unconventional Reservoirs.

The traditional guar gum fracturing fluid system has the drawbacks of the fracturing process of unconventional oil and gas deposits, such as high drag resistance and large residuum harm, which is gradually replaced by the system of the slick water fracturing fluid. The conventional slick water system, however, still has the features of low sand-carrying capability. Therefore, high-viscosity slick water is often used in fracturing operations, but most of the high-viscosity slick water is difficult to prepare, dissolve, and break gels, which needs to be improved. Based on the abovementioned problems, a new type of multifunctional variable-viscosity slick water is proposed in this paper. The self-made loop drag test unit, a dynamic crack sand-carrying model, a multifunctional core flow device, and other equipment were used for testing, and a set of systematic evaluation methods for the performance of multifunctional variable-viscosity slick water are established. In addition, the mechanism of improving sand-carrying capacity and increasing viscosity and solubilization was explained through the macroevaluation experiment of polymer properties and the analysis of the polymer microstructure. The experimental results show that compared with high-viscosity slick water, the multifunctional variable-viscosity slick water has good drag-reducing performance, the drag-reducing rate can reach more than 75%; the intersection value of viscoelastic modulus is about 0.01 Hz, the sand carrying capacity is higher; the gel-breaking time is faster, the residue content is lower, 38.5 ppm; it has the characteristics of low harm, the harm rate to the core is 18.30%; and it also has the performance of enhancing oil recovery.

Study on the Mechanism of Nanoemulsion Removal of Water Locking Damage and Compatibility of Working Fluids in Tight Sandstone Reservoirs.

The invasion of external fluids, because of hydraulic fracturing for tight sandstone gas reservoirs, will cause the decrease of fracture conductivity and rock matrix permeability and decrease the flow of oil and gas. The nanoemulsion has a smaller molecular size and is used in combination with the fracturing fluid. After entering the formation, it can reduce the surface tension of gas/water, change the wettability of the rock surface, and improve the flowback rate of the fracturing fluid. In this study, a set of systematic evaluation methods was established in the laboratory to evaluate the mechanism and effect of removal of water locking additive in tight sandstone gas reservoirs. The adsorption experimental results of the nanoemulsion on the rock surface show that the adsorption of the nanoemulsion on the solid-phase particle surface is from strong to weak in the order of smectite, kaolinite, DB105X well rock powder, quartz sand, illite, chlorite, and ceramsite proppant. The experiment on the influence of the nanoemulsion on the spontaneous imbibition of reservoir rocks shows that when the gas permeability of reservoir rocks is K g < 5.0 mD, adding a nanofluid in the working fluid to change the wettability of reservoir rocks can effectively reduce the imbibition and retention of external fluids in reservoir rocks, thus reducing the "water locking damage". When the gas permeability of reservoir rocks is 5.0 mD < K g ≤ 1.0 D, the effect of changing the reservoir wettability to prevent the "water locking damage" is reduced. At the same time, the nanoemulsion has good compatibility with different types of fracturing fluid and is beneficial for improving the flowback rate.

Unusual regio- and stereo-selectivity in Diels-Alder reactions between bulky N-phenylmaleimides and anthracene derivatives.

Unusual regio- and stereo-selectivity in Diels-Alder (D-A) reactions were achieved between bulky N-phenylmaleimides and anthracene derivatives. Using multiple substituents with steric hindrance on both diene and dienophile, a noticeable shift toward 1,4-addition was successfully obtained. The substrate scope in this reaction was broad and the highest yield of anti-1,4-adducts was over 90%. Novel structures of anti-1,4-adducts were confirmed by single crystal X-ray diffraction analysis. This study not only provides the first reported method of synthesizing anti-1,4-adducts and achieving otherwise unattainable regio- and stereo-selectivity, but also elucidates the importance of combining the steric effects of two reactants to shift products toward 1,4-adducts. Moreover, the resulting 1,4-adducts could be further functionalized through their halogen groups via carbon-carbon coupling reactions.

Measuring the distance between two mercapto groups with an optical molecular ruler on the nanometer scale.

We have developed an absorption spectrum based molecular ruler that measures the distance between two mercapto groups. The conformation of the molecular rulers changes with the distance, which induces an absorption spectrum change. DFT calculation has been carried out to elucidate the relation between the molecular conformation and the absorption spectrum. With this simple method, we can estimate the distance between two mercapto groups on the scale of 0.4-1 nm. This method can also be used to monitor conformation transition, which is demonstrated by a silver ion titration experiment.