Performance and Mechanisms of Zwitterionic Polymer Modified Nanoparticles in Calcium Resistance, Plugging and Filtration Control
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摘要: 为解决水基钻井液抗温抗钙封堵问题，基于“反聚电解质效应”相关理论，通过在二氧化硅纳米颗粒表面接枝两性聚合物，得到了适应高温高钙钻井环境封堵性纳米颗粒ZP-NPs。借助红外光谱、电镜观察确认其微观结构，通过分散稳定、滤失实验、封堵实验评价其性能。结果表明：ZP-NPs在高温高浓度钙盐水（160℃，11%CaCl2）中长期保持纳米级/亚微米级稳定分散，含ZP-NPs的基浆受高浓度钙污染后高温高压（160℃、3.5 MPa）滤失量不超过 20 mL、滤饼薄而致密，协同膨润土封堵5 μm裂缝可承受5.5 MPa。通过粒径分析、能谱元素分析揭示了ZP-NPs抗钙封堵降滤失机理：ZP-NPs具有强的“反聚电解质”效应，在高钙条件下仍保持纳米粒径分布，并且能屏蔽钙离子在膨润土颗粒上的吸附、改善膨润土浆的抗钙分散稳定性，由此使得膨润土浆在高钙条件下保持优异的降滤失性能。该研究成果为抗钙封堵剂新材料研发提供了新的理论与技术指导。Abstract: A high temperature calcium resistant plugging agent ZP-NPs has been developed based on the “anti-polyelectrolyte effect” theory to render water based drilling fluids high temperature stability, high calcium resistance and good plugging capacity. ZP-NPs is obtained by grafting zwitterionic polymer molecules onto the surfaces of nano silica. The microstructure of ZP-NPs was observed using infrared spectrum and electroscope, and the performance of ZP-NPs evaluated through dispersion test, filtration test and plugging test. It was found in these tests that ZP-NPs can stably disperse to nanoparticles/submicron particles for a long time in a high temperature high calcium chloride concentration (160℃, 11%CaCl2) solution. A base slurry, after being contaminated by high concentration calcium ions, has a high temperature high pressure (160℃, 3.5 MPa) filtration rate that does not exceed 20 mL, and the mud cakes obtained from the test are thin and tough. Fractures of 5 μm in width plugged by a bentonite slurry treated with ZP-NPs can stand pressures up to 5.5 MPa. The calcium resistant performance, plugging capacity and filtration control property of ZP-NPs were revealed through particle size analysis and EDS, and it was found that ZP-NPs has strong “anti-polyelectrolyte” effect; at high calcium concentrations, the particle sizes of ZP-NPs are still in nanometer size range, they can effectively shield the bentonite particles against the adsorption of calcium ions, thus maintaining the dispersion stability and excellent filtration control performance of a bentonite slurry at high calcium concentrations. This study provides a new theoretical and technical guidance for the development of new plugging agents with good calcium resistant capacity.
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图 6 ZP-NPs对11%氯化钙基浆滤饼质量的影响
注：a.11%氯化钙基浆，API滤饼；b. 氯化钙基浆+2.5% ZP-NPs，API滤饼；c. 氯化钙基浆+2.5%ZP-NPs，HTHP滤饼（160℃、3.5 MPa）
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