Study on Mechanism of the Fracturing Fluid Performance Improvement and Oil Displacement Using Nanomaterials
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摘要: 为给研发功能性压裂液提供理论依据，在纳米尺度（50 nm）对SiO2进行C8和季铵盐（QAS）修饰，合成了疏水纳米材料SiO2-C8和疏水带电纳米材料SiO2-QAS，评价了SRFP型聚合物清洁压裂液分别加入SiO2，SiO2-C8及SiO2-QAS等3种纳米材料后的配伍性、稳定性及综合性能；利用量化模拟手段，建立了纳米材料在砂岩表面的吸附结构模型及吸附动力学模型，分析了纳米材料在砂岩表面的吸附及油水分离特征。试验及模拟结果表明：SiO2，SiO2-C8及SiO2-QAS等3种纳米材料在压裂液中具有较好的分散稳定性，可有效降低表界面张力，表现出良好的耐温、耐剪切性能；SiO2-C8和SiO2-QAS加入压裂液后有利于砂岩表面油分子被置换出，促进油水分离；SiO2-C8和SiO2–QAS加入压裂液后可有效改善压裂液性能，提高驱油效果，降低压裂液波及范围内的含油饱和度。研究结果可为功能性压裂液发展和研制提供理论依据，为优化致密油、页岩油压裂方案和优选压裂液提供参考。Abstract: To provide a theoretical basis for the development of functional fracturing fluids, SiO2 was modified with C8 and quaternary ammonium salt (QAS) on nanoscale (50 nm). The hydrophobic nanomaterial SiO2-C8 and hydrophobic charged nanomaterial SiO2-QAS were synthesized. The compatibility, stability, and comprehensive performance of the SRFP polymer clean fracturing fluid systems were evaluated as nanomaterials SiO2, SiO2-C8, and SiO2-QAS were added. Quantitative simulation methods were employed to build the adsorption structure models and adsorption kinetics models of the nanomaterials on the sandstone surface. The adsorption and oil-water separation characteristics of nanomaterials on sandstone surfaces were analyzed. The experimental and simulation results show that the three nanomaterials, SiO2, SiO2-C8, and SiO2-QAS, display favorable dispersion stability in fracturing fluids. They can effectively reduce the surface and interfacial tension and demonstrate good temperature and shear resistance. SiO2-C8 and SiO2-QAS nanomaterials are beneficial to the replacement of oil molecules on the sandstone surface and the oil-water separation when they are added into fracturing fluids. The addition of nanomaterials SiO2-C8 and SiO2-QAS can also effectively improve the performance of fracturing fluids, enhance oil displacement, and reduce oil saturation within the spread range of fracturing fluids. The research results can provide a theoretical basis for the development of functional fracturing fluids and a reference for fracturing design optimization and fracturing fluid selection for tight oil and shale oil.
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图 1 单分散纳米SiO2球形颗粒的形成过程
Figure 1. Formation process of monodisperse spherical nano-SiO2 particles
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图 7 中黏SRFP型清洁压裂液的流变曲线
Figure 7. Rheological curve of medium-viscosity SRFP clean fracturing fluids
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图 8 中黏纳米驱油压裂液的流变曲线
Figure 8. Rheological curve of medium-viscosity nano oil displacement fracturing fluids
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图 10 固定后的（12×3×1）α-SiO2（010）面物理模型
Figure 10. Physical model of fixed (12×3×1)α-SiO2(010) surface
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图 11 SiO2-C8在α-SiO2（010）面的吸附结构模型
Figure 11. Adsorption structure model of SiO2-C8 on α-SiO2(010) surface
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图 12 SiO2-QAS在α-SiO2（010）面的吸附结构模型
Figure 12. Adsorption structure model of SiO2-QAS on α-SiO2(010) surface
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图 13 SiO2-C8在砂岩表面的吸附聚集过程
Figure 13. Adsorption and deposition process of SiO2-C8 on the sandstone surface
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图 14 SiO2-QAS在砂岩表面的吸附聚集过程
Figure 14. Adsorption and deposition process of SiO2-QAS on the sandstone surface
表 1 低黏清洁压裂液加入纳米材料前后的表面张力
Table 1 Surface tension before and after nanomaterials added to low-viscosity clean fracturing fluids
mN/m 纳米材料加量，% 压裂液 SiO2 SiO2-C8 SiO2-QAS 0.1 33.6 17.7 22.3 28.8 0.5 15.7 20.7 23.0 1.0 13.8 20.2 22.4 2.0 12.5 18.6 24.2 
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表 2 低黏清洁压裂液加入纳米材料前后的表界面张力
Table 2 Surface and interfacial tension before and after nanomaterials added into low-viscosity clean fracturing fluids
纳米材料 表面张力/（mN·m–1） 界面张力/（mN·m–1） 加入前 加入后 加入前 加入后 SiO2 33.6 15.7 2.858 0.212 SiO2-C8 33.6 20.7 2.858 0.239 SiO2-QAS 33.6 23.0 2.858 0.256
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表 3 C6H14、SiO2-C8、SiO2-QAS在α-SiO2（010）面的吸附能
Table 3 Adsorption energy of C6H14, SiO2-C8 and SiO2-QAS molecules on the α-SiO2(010) surface
M Ead（SiO2-M）/eV Et（SiO2-M）/eV Et（SiO2）/eV Et（M）/eV C6H14 –1 722 287.31 –6 388.85 –1 715 896.91 –1.54 SiO2-C8 –1 777 032.99 –61 132.64 –1 715 896.91 –3.44 SiO2-QAS –1 803 366.81 –87 460.07 –1 715 896.91 –9.83
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