Fabrication of Bifunctional TiO2/POM Microspheres Using a Layer-by-Layer Method and Photocatalytic Activity for Methyl Orange Degradation

Bifunctional films of Keggin-type polyoxometalates H3PW12O40 (PW12), H4SiW12O40 (SiW12), H3PMo12O40 (PMo12), and TiO2 were successfully built on Fe3O4@SiO2 microspheres using a layer-by-layer method. The characterization by field emission scan electronic microscopy (FESEM) and energy dispersive X-ray spectroscopy (EDX) shows that TiO2 nanoparticles and polyoxometalate (POM) anions are successfully assembled. The photodegradation of methyl orange (MO) was used to test the photocatalytic efficiency of magnetic catalysts under UV irradiation. For MO decomposition, multilayer films that combine PW12 and SiW12 with TiO2 show high efficiency, which can be attributed to the synergistic effect between POMs and TiO2. The degradation of the model contaminant was also systematically checked under different conditions such as bilayer number deposited on magnetic microspheres, catalyst concentration, inorganic oxidants, and salts. The oxidation process of MO follows an apparent first-order reaction. Furthermore, the composite catalysts deposited on Fe3O4@SiO2 magnetic microspheres can be conveniently, quickly, and efficiently separated by an external magnet from a solution

Experimental Study of Fracturing Fluid Retention in Rough Fractures

Multistage hydraulic fracturing is a key technology for developing tight reservoirs. Field data indicate that a small fraction of the injected water can be recovered during flowback. Fractures play an important role in the retention of fracturing fluid, but the mechanisms and rules remain uncertain. Therefore, an experimental facility was established for studying the fluid retention in fractures using an improved conductivity apparatus. The fluid trapped in rough fractures was measured, and the dynamic changes of the drainage volume and rate under various apertures were analyzed. The effects of different factors, such as the fracture aperture, surface roughness, tortuosity, and matrix imbibition, on the fluid retention were studied. An empirical formula between the retention rate and fracture aperture was derived on the basis of mass conservation. Results showed that the fluid retention rate slowly decreased with an aperture increase in the fracture, and it would increase with considerable roughness, high tortuosity, and significant matrix imbibition. Meanwhile, drainage volume and rate change dramatically resulted from the gas drive. Secondary fractures and microcracks played an important role in the retention of fracturing fluid. Furthermore, the mechanisms of fracturing fluid retained in the tight reservoir, including viscous trapping and “locking” in fractures, the effect of gravity, surface-bound water film, capillary force retention, and matrix imbibition, were discussed. This study is significant for understanding the flowback rules of fracturing fluid, diagnosing fracture development, and identifying reservoir properties

Quantitative Evaluation of Synsedimentary Fault Opening and Sealing Properties using Hydrocarbon Connection Probability Assessment

Hydraulic behaviors of faults in sedimentary basins have been paid close attention in studies of hydrocarbon migration and accumulation because of their important functions in basin hydraulic circulations. In previous studies, however, the function of faults in hydrocarbon migration is characterized by the sealing capacity of faults. In fact, sealing is only an impressive and time-dependent aspect of the hydraulic behavior of faults, which may act as seals during some periods and as pathways some time later. Therefore, in hydrocarbon migration studies, sealing indices may successfully be used in some cases but not in others. In this article, we introduce an empirical method (termed the fault-connectivity probability method) for assessing the hydraulic connecting capacity of a fault for hydrocarbon migration over geological time scales. The method is based on the recognition that observable hydrocarbon in reservoirs should result from the opening and closing behavior of the fault during the entire process of hydrocarbon migration. In practice, the cumulative petroleum migration through a segment of the fault zone is identified by the presence (or not) of hydrocarbon-bearing layers on both sides of the segment. Data from the Chengbei step-fault zone (CSFZ) in the Qikou depression, Bohai Bay Basin, northeast China, were used to develop this method. Fluid pressure in mudstones, normal stress perpendicular to fault plane, and shale gouge ratio are identified as the key factors representing fault-seal capacity. They are combined to define a nondimensional fault opening index (FOI). The values of FOI are calculated from the measured values of the key factors, and the relationship between FOI and fault-connectivity probability on any fault segment is established through statistical analysis. Based on the data from the CSFZ, when the FOI is less than 0.75, the fault-connectivity probability is 0; when FOI ranges from 0.75 to 3.25, the corresponding fault-connectivity probability increases from 0 to 1 following a quadratic polynomial relationship; when FOI is greater than 3.25, the fault-connectivity probability is 1. The values of fault-connectivity probability can be contoured on a fault plane to characterize the variations of hydraulic connective capacity on the fault plane. The applicability of this concept for other oil fields (in particular, the quantitative relationship between FOI and fault-connectivity probability) has still to be ascertained

Medium-deep clastic reservoirs in the slope area of Qikou sag, Huanghua depression, Bohai Bay Basin

To get a better understanding of the distribution pattern of favorable reservoir belts in the medium-deep clastic rocks in the Qikou sag of the Huanghua depression, and find out premium reservoir zone, the characteristics and controlling factors of the medium-deep reservoirs in the Qikou sag were analyzed. Comprehensive study into the structural setting, provenance, depositional system, and reservoir properties shows that the Paleogene in the Qikou sag has multi-sags and multi-slopes, with slopes accounting for over 70% of the total sag area. A number of large braided river (fan) delta front - gravity flow sand bodies matching with multi-slope zones lay a good material foundation for the formation of medium-deep effective reservoirs there. Generally buried at over 2500 m, the medium-deep clastic rocks are lithic feldspathic sandstone, with secondary pores and cracks as major reservoir space. Being in the medium diagenesis evolution stage, the medium-deep clastic rocks in the Qikou sag span over a large depth. Nine major factors affecting reservoir properties have been identified by mathematical geology. Although the medium-deep clastic rock interval is poor in physical properties and complex in pore structure, high sedimentation rate, medium geothermal field, high fluid pressure, high feldspar content, relatively high dissolution rate and early oil and gas charge have given rise to three to four belts with abnormally high porosity in it, which are all favorable hydrocarbon reservoir zones. Key words: slope area, medium-deep clastic, oil and gas reservoir, diagenetic evolution, Paleogene, Qikou sag, Bohai Bay Basi