Preparation and Performance Evaluation of Novel Organoclay for Oil-based Drilling Fluids
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摘要: 为提升油基钻井液在高温下的流变性能，以膨润土为基质，对比探究头基结构（季铵、吡啶、咪唑）与烷基链长对有机土的微观结构和高温流变性能的影响规律。FT-IR、XRD和热重结果表明，改性剂均通过头基静电吸附/尾链疏水作用插层于膨润土层间或物理吸附于表面，CTAC、OPB、CPB、OMB与CMB通过物理吸附/静电插层在膨润土上的最大负载量分别为0.37/0.56 、0.021/0.63、0.44/0.28、0.016/0.54、0.17/0.48 mmol/g。分子动力学模拟结果表明，高温下CPB的静电能绝对值由87.42增至88.17 kcal/mol，这与高温促进CPB与膨润土间静电作用有关。流变实验结果表明，从头基结构来看，杂环改性有机土展示出较好的高温流变性能，240 ℃热滚后OBen-3的表观黏度和动切力分别可达19 mPa·s和3 Pa；从烷基链长来看，有机土的流变性能随链长增加而大幅提升。在全油基钻井液体系中，240 ℃热滚后，OBen-3的表观黏度、塑性黏度和动切力分别为90 mPa·s、85 mPa·s和5 Pa，展现出良好的配伍性与高温流变性能。同时，OBen-3高温高压滤失量仅为3.2 mL，具有良好的降滤失性能。此外，OBen-3在油包水体系中也展现出良好的高温流变性能与高温高压降滤失性能。研究表明，引入长烷基链刚性结构可增强分子间以及有机土结构间界面作用，显著提升有机土的高温流变性能，为抗高温油基钻井液用有机土开发提供思路。Abstract: To improve the rheological performance of oil-based drilling fluids at high temperatures, bentonite was used as the matrix to comparatively investigate the effects of head-group structures, including quaternary ammonium, pyridine, and imidazole groups, and alkyl chain length on the microstructure and high-temperature rheological performance of organoclays. FT-IR, XRD, and thermogravimetric analyses showed that the modifiers were intercalated into the bentonite interlayers through electrostatic adsorption of the head groups and hydrophobic interactions among the tail chains, while some were physically adsorbed onto the surface. The maximum physical adsorption/electrostatic intercalation loadings of CTAC, OPB, CPB, OMB, and CMB on bentonite were 0.37/0.56 mmol/g, 0.021/0.63 mmol/g, 0.44/0.28 mmol/g, 0.016/0.54 mmol/g, and 0.17/0.48 mmol/g, respectively. Molecular dynamics simulations indicated that the absolute value of the electrostatic energy of CPB increased from 87.42 kcal/mol to 88.17 kcal/mol under high-temperature conditions, suggesting enhanced electrostatic interactions between CPB and bentonite. Rheological experiments showed that, with respect to head-group structures, heterocyclic-group-modified organoclays exhibited better high-temperature rheological performance, with the AV and YP of OBen-3 reaching 19 mPa·s and 3 Pa, respectively, after hot rolling at 240 ℃. As the alkyl chain length increased, the rheological performance of the organoclays improved markedly. After hot rolling at 240 ℃ in the all-oil-based drilling fluid system, OBen-3 exhibited AV, PV, and YP values of 90 mPa·s, 85 mPa·s, and 5 Pa, respectively, demonstrating good compatibility and high-temperature rheological performance. Moreover, the high-temperature and high-pressure filtration loss of OBen-3 was only 3.2 mL, indicating good filtration-loss control performance. In addition, OBen-3 exhibited favorable high-temperature rheological performance and effective high-temperature and high-pressure filtration-loss control in the water-in-oil system. This study suggests that introducing rigid structures with long alkyl chains can enhance intermolecular and interfacial interactions within the organoclay structure, thus significantly improving the high-temperature rheological performance of organoclays. These findings provide insights into the development of organoclays for high-temperature-resistant oil-based drilling fluids.
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Key words:
- Oil-based drilling fluid /
- Organoclay /
- Bentonite /
- Surfactant /
- Rheological performance
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表 1 有机膨润土在240 ℃热滚前后的流变性和胶体率
样品 实验条件 AV/
mPa·sPV/
mPa·sYP/
Pa胶体率/
%OBen-1 热滚前 13.5 10 3.5 100 240 ℃ × 16 h 16.5 14 2.5 100 OBen-3 热滚前 11.5 9 2.5 100 240 ℃ × 16 h 19.0 16 3.0 100 OBen-5 热滚前 13.5 10 3.5 100 240 ℃ × 16 h 21.0 18 3.0 100 
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表 2 有机膨润土在240 ℃热滚前后的流变性和胶体率
样品 实验条件 AV/
mPa·sPV/
mPa·sYP/
Pa胶体率/
%OBen-2 热滚前 9.0 8.5 0.5 50 240 ℃ × 16 h 8.5 8.0 0.5 96 OBen-3 热滚前 11.5 9.0 2.5 100 240 ℃ × 16 h 19.0 16.0 3.0 100 OBen-4 热滚前 9.0 8.5 0.5 94 240 ℃ × 16 h 8.5 8.0 0.5 96 OBen-5 热滚前 13.5 10.0 3.5 100 240 ℃ × 16 h 21.0 18.0 3.0 100
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表 3 3种全油基体系240 ℃热滚前后的流变性与降滤失性
样品 实验条件 AV/
mPa·sPV/
mPa·sYP/
PaFLHTHP/
mL2.5%OBen-1 热滚前 79.0 73 6.0 − 240 ℃×16 h 85.0 82 3.0 − 2.5%OBen-3 热滚前 81.0 73 8.0 − 240 ℃×16 h 90.0 85 5.0 3.2 2.5%OBen-5 热滚前 74.0 69 5.0 − 240 ℃×16 h 81.5 79 2.5 − 注：FLHTHP在200 ℃、3.5 MPa下测定。
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表 4 油包水体系240 ℃热滚前后流变性能与降滤失性能
样品 实验条件 AV/
mPa·sPV/
mPa·sYP/
PaFLHTHP/
mL3%OBen-3 热滚前 41.5 35 6.5 − 240 ℃×16 h 81.5 72 9.5 5 注：FLHTHP在200 ℃、3.5 MPa下测定。
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表 5 不同温度下改性剂与膨润土的吸附能
改性剂 T/K 吸附能/（kcal·mol−1） 总吸附能 范德华能 静电能 CPB 298 −114.86 −26.67 −87.42 513 −113.98 −25.04 −88.17
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