Center of Innovation for Flow through Porous Media, University of Wyoming, 1000 E. University Ave., Laramie, Wyoming82071, United States.
Carl Zeiss Shanghai Co. Ltd., 60 Mei Yue Road, Shanghai200131, China.
Langmuir. 2023 Feb 7;39(5):1870-1884. doi: 10.1021/acs.langmuir.2c02900. Epub 2023 Jan 24.
The in situ change in oil flow behavior inside propped fractures due to wettability alteration of proppant grains and fracture surfaces was thoroughly investigated for the first time in this study. A series of microscale flow experiments were performed in mixed-wet fractured and propped miniature ultra-tight carbonate cores where the effect of wettability on oil bridging and fracture oil layer integrity was probed during oil production. During the initial production, proppant wettability changed toward an intermediate-wet state (contact angle (CA) = 96°) while that of fracture surfaces became strongly oil-wet (CA = 139°). Consequently, the fracture oil layer grew in size on both fracture surfaces and imbibed into the proppant pack through piston-like displacement and pore body filling until oil bridges were formed during oil injection. However, subsequent waterflooding induced thinning and rupturing of those bridges due to the accompanying reduction in the threshold capillary pressure of the proppant at higher aging times. The in situ chemical treatment of the proppant by a cationic surfactant (dodecyl tri-methyl ammonium bromide) could reverse its wettability toward weakly water-wet state (CA = 78°) after oil solubilization from the sand grains followed by substitutive surfactant adsorption. Surfactant injection also impacted the wettability of the fracture surface due to oil solubilization, reducing its mean contact angle down to an intermediate range (CA = 99°). As a result, the following oil production cycle yielded a smaller fracture oil layer. The surfactant effect on proppant wettability lasted for 2 weeks while its effect on fracture wettability lasted for more than 6 weeks. Similar flow cycles were performed with an anionic nanoparticle (graphene quantum dot) with hydrogen bonding ability. The nanoparticle solution yielded a quick reduction of the proppant and fracture surface contact angles to nearly 77° and 115°, respectively. Proppant wettability alteration occurred because the nanoparticles self-assembled at the three-point contact region between adsorbed oil and quartz surfaces, leading to oil solubilization in intermediate-wet regions while oil-wet regions remained unchanged. Therefore, re-introducing oil into the fracture instantaneously re-instated the initial wettability state of proppant grains (CA = 88°), deeming the nanoparticle solution ineffective. This study revealed that oil production through hydraulic fractures can be enhanced by monitoring the wettability of the proppant pack. If the production has a high water cut, it is beneficial to use chemical agents that reduce the proppant contact angles to a weakly water-wet state in order to preserve the hydraulic conductivity of the oil layer.
本研究首次彻底研究了由于支撑剂颗粒和裂缝表面润湿性的变化,支撑裂缝内部油流行为的原位变化。在混合润湿和支撑的微型超紧密碳酸盐岩岩心内进行了一系列微尺度流动实验,在开采过程中探究了润湿性对油桥接和裂缝油层完整性的影响。在初始生产过程中,支撑剂的润湿性向中等润湿状态(接触角(CA)=96°)转变,而裂缝表面的润湿性变得强烈油润湿(CA=139°)。因此,裂缝油层在两个裂缝表面上的尺寸增大,并通过活塞状位移和孔隙体填充吸入支撑剂包装中,直到在注油期间形成油桥。然而,随后的注水由于在更高的老化时间下支撑剂的临界毛管压力降低,导致这些桥的变薄和破裂。通过阳离子表面活性剂(十二烷基三甲基溴化铵)对支撑剂进行原位化学处理,可以在油从砂粒中溶解后,使支撑剂的润湿性反向变为弱水润湿状态(CA=78°),然后进行取代性表面活性剂吸附。表面活性剂注入也会由于油的溶解而影响裂缝表面的润湿性,将其平均接触角降低到中间范围(CA=99°)。因此,下一个采油周期产生的裂缝油层较小。表面活性剂对支撑剂润湿性的影响持续了 2 周,而对裂缝润湿性的影响持续了 6 周以上。用具有氢键能力的阴离子纳米颗粒(石墨烯量子点)进行了类似的流动循环。纳米颗粒溶液使支撑剂和裂缝表面的接触角迅速降低到接近 77°和 115°。支撑剂润湿性的改变是因为纳米颗粒在吸附油和石英表面之间的三点接触区域自组装,导致中间润湿区域的油溶解,而油润湿区域保持不变。因此,将油重新引入裂缝中,可立即恢复支撑剂颗粒的初始润湿性状态(CA=88°),使纳米颗粒溶液失效。本研究表明,通过监测支撑剂包装的润湿性,可以增强水力裂缝的采油。如果生产具有高含水率,则使用可将支撑剂接触角降低至弱水润湿状态的化学剂将有利于保持油层的水力传导率。