Hongxing Xu

China hosts abundant coal-rock gas (CRG) resources, which have become a critical unconventional natural gas contributor to national reserve expansion and production increment. Supercritical carbon dioxide (ScCO₂) fracturing is recognized as a green and efficient stimulation technology, exhibiting great potential for high-efficiency CRG exploitation. To clarify the effects and intrinsic mechanisms of ScCO₂ treatment on coal fracture initiation, propagation, and CRG recovery enhancement, true triaxial fracturing and CO₂-CH₄ displacement experiments were performed in combination with multiple microscopic characterization methods, including X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and Scanning electron microscopy (SEM). The multi-scale experimental investigation systematically revealed the fracture development mechanism, permeability variation characteristics, and microstructural evolution of coal reservoirs under ScCO₂ interactions. The results indicate that ScCO₂ fracturing significantly lowers the coal fracture initiation threshold compared with conventional hydraulic fracturing, with the breakdown pressure reduced by 26.2% and the initiation time shortened by 37.5%. Such advantages facilitate coal fracture activation and the development of complex fracture networks. Long-term ScCO₂ soaking induces the dissolution of inorganic minerals (e.g., calcite, plagioclase, and clay minerals) and the extraction of inherent organic matter within coal matrices. The coupled hydro-chemical reactions reconstruct the coal pore structure, enlarge pore throats, and improve reservoir permeability, achieving a maximum permeability enhancement of approximately 1.6 times. Meanwhile, ScCO₂ displacement yields a prominent CRG recovery performance, with an ultimate gas recovery factor up to 93.85%. The CRG enhancement mechanism of ScCO₂ fracturing is comprehensively attributed to three core coupled effects. First, ScCO₂ dynamic fracturing generates intricate fracture networks, which greatly optimize reservoir seepage channels and flow space. Second, the ScCO₂–formation water–coal interaction modifies coal physical properties via mineral dissolution and organic matter extraction, thereby improving reservoir permeability. Third, the preferential adsorption of CO₂ over CH₄ triggers effective competitive adsorption and gas displacement, further promoting adsorbed methane desorption and elevating CRG recovery efficiency. This study provides a solid theoretical foundation for the field application of ScCO₂ fracturing technology and offers valuable insights into the green, efficient, and sustainable development of deep coal-rock gas resources.

In this paper, to remove the water lock effect in tight gas reservoirs, amphipathic polymer-modified titanium quantum dots (PTQs) were synthesized via in situ polymerization, showing a hyper-branched structure and an excellent synergistic effect with the nonionic fluorocarbon surfactant to break the water lock. The molecular structure, fluorescent property, and micromorphology of the PTQs were obtained. The surface activity and wettability alteration of rock are discussed. Results show that PTQs have zwitterionic hydrophilic groups and the hydrophobic structure of long-chain groups on their molecular structure. PTQ fluid, with a median particle size of 3.6 nm, showed strong green fluorescence and had excellent dispersibility in 50,000 mg/L of standard saline fluid at 120 °C. Additionally, the surface tension decreased to 18.6 mN/m at a PTQ concentration of 0.08%. At a 0.1% concentration, PTQ fluid altered the water wettability of tight sandstone to 67.2°, which resulted in lower capillary resistance. Furthermore, the surfactant (PHPE) had a good synergistic effect with the PTQs to decrease surface tension and alter the wettability of the sandstone surface, leading to lower surface tension and significant amphiphobicity. The strong surface activity of PTQs results from their specific molecular structure, which enables electrostatic attraction, quantum size effects, hydrogen bonding, and van der Waals forces between the inter-polar molecules of PTQs and the surface of sandstone to forcefully eliminate the water lock effect. This study offers key guidance for the development of a high-performance water-lock-breaking agent and application of titanium quantum dots in tight gas reservoirs.

Coal-bed gas well production is too low to realize a highly efficient exploitation of the #8 coal seam in the Shanxi formation in the Nalin region. Based on the reservoir characteristics, the designed poly-aromatic-grafted silicon-quantum-dot-based desorption agent (PQS) has been developed. Then, the adsorption/desorption behavior of CBM on the coal surface under the influence of this active chemical has been studied, and the synergy effect with an anionic–nonionic surfactant to desorption of CBM has also been discussed. The results show that the developed poly-aromatic-grafted silicon quantum dot, with a median size of 4.9 nm and +5.6 mV of zeta potential in neutral condition, has a significant emission peak with 470 nm at the excitation of 380 nm and 150,000 mg/L of salinity resistance, which also generates a strong adsorption capacity on the coal surface. A promoting effect to desorption of CBM for PQS nanofluid is exhibited and the Langmuir pressure is obviously increased. However, when the PQS nanofluid is synergized with an anionic–nonionic surfactant, the desorption of CBM is further improved and the wettability of the coal surface is altered from 78.2° to 84.2°. The desorption rate for this compound system reached 65.3%. It can be found that combining the quantum size, π–π stacking, π–π conjugation, and the synergy effect between PQS nanofluid and surfactant fluid with the traditional intermolecular force has a stronger capacity for promoting desorption of CBM than the conventional desorption agent. This study provides guidance for the molecular design of the desorption agent for deep coal rock and the application of silicon quantum dots.