表面功能化1t相二硫化钼纳米片改善酸性低聚合物负载锆交联CMHPG压裂液的凝胶性能

Kaiyu Zhang, J. Hou, Zhuojing Li
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引用次数: 0

摘要

中国的低、特低渗透油藏,如长庆、冀东、大庆外围油田,通常采用CO2作为驱油介质来提高采收率。高温高压条件下,CO2、地层岩石和地层水之间会发生一系列水岩相互作用。地层的pH值将相应地转化为酸度。作为一个副作用,传统的碱性瓜尔胶压裂液,如硼酸盐交联羟丙基瓜尔胶(HPG),由于不相容,无法实现有效的水力压裂作业。因此,开发一种性能令人满意的酸性压裂液体系势在必行。酸性压裂液,如锆交联羧甲基羟丙基瓜尔胶(CMHPG),可以在水力压裂过程中保护地层免受粘土颗粒膨胀和运移造成的损害。然而,酸性压裂液粘度增长不可控、剪切变薄不可逆等缺点限制了酸性压裂液的大规模应用。本文利用实验室合成的新型有机锆交联剂控制和延缓了酸性条件下的交联反应。与锆中心配位的配体是l -乳酸和乙二醇。使用的增稠剂是低负荷0.3%(约25 pptg)的CMHPG。同时,利用表面功能化金属相(1t相)二硫化钼(MoS2)纳米片改善锆交联CMHPG压裂液的流变性能。修饰试剂为l -半胱氨酸。利用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、拉曼光谱、x射线衍射(XRD)、x射线光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)和热重分析(TGA)等手段对制备的功能化1T-MoS2 (Cys-1T-MoS2)纳米片的形貌、结构和性能进行了系统表征。表征测试的结果表明,l -半胱氨酸成功地功能化了1T-MoS2纳米片。然后,在控制应力或控制速率模式下,采用Sydansk瓶测试方法结合流变仪,系统地评估了不同交联剂和纳米片载荷的新型纳米片增强锆交联CMHPG压裂液体系对凝胶性能的影响。结果表明,纳米片增强压裂液具有良好的延迟性能。与空白压裂液(不含纳米片)相比,纳米片增强压裂液具有更好的抗剪切性能和剪切恢复性能。
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Improved Gelation Performance of an Acidic Low-Polymer Loading Zirconium Cross-Linked CMHPG Fracturing Fluid by Surface Functionalized 1T-Phase Molybdenum Disulfide Nanosheets
The low and ultra-low permeability reservoirs in China, such as the Changqing, Jidong, and Daqing peripheral oil fields, often apply CO2 as a flooding medium to enhance oil recovery. A serial of water-rock interactions will be occurred among the CO2, formation rock, and formation water under the HT/HP conditions. The pH value of the formation will be converted to acidity accordingly. As a side effect, the traditional guar-based fracturing fluids in an alkaline range, such as the borate cross-linked hydroxypropyl guar gum (HPG), cannot result in an effective hydrofracturing operation due to the incompatibility. Consequently, developing an acidic fracturing fluid system with a satisfactory performance is an imperative. Acidic fracturing fluids, such as the zirconium cross-linked carboxymethyl hydroxypropyl guar gum (CMHPG), can protect the formation during the hydrofracturing process from the damage arising from the swelling and migration of the clay particles. However, the shortcomings of the uncontrollable viscosity growth and the irreversible shear-thinning behavior limit the large-scale use of the acidic fracturing fluids. In this work, a novel organic zirconium cross-linker synthesized in the laboratory was applied to control and delay the cross-link reaction under the acidic condition. The ligands coordinated to the zirconium center were the L-lactate and ethylene glycol. The thickener used was the CMHPG at a low loading of 0.3% (approximately 25 pptg). Meanwhile, the surface functionalized metallic phase (1T-phase) molybdenum disulfide (MoS2) nanosheets were employed to improve the rheological performance of the zirconium cross-linked CMHPG fracturing fluid. The modification reagent utilized was the L-cysteine. The morphology, structure, and property of the fabricated functionalized 1T-MoS2 (Cys-1T-MoS2) nanosheets were systematically characterized using the transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) measurements. The results of the characterization tests demonstrated a successful functionalization of the 1T-MoS2 nanosheets with L-cysteine. Then, the effects of this new nanosheet-enhanced zirconium cross-linked CMHPG fracturing fluid systems with different cross-linker and nanosheet loadings on gelation performance were systematically assessed employing the Sydansk bottle testing method combined with a rheometer under the controlled-stress or controlled-rate modes. The results indicated that the nanosheet-enhanced fracturing fluid had a desirable delayed property. Compared with the blank fracturing fluid (without nanosheets), the nanosheet-enhanced fracturing fluid had a much better shear-tolerant and shear-recovery performance.
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