An Amphoteric Copolymer Coated Carbon Nanotube Low Viscosity Filter Loss Reducer with High Cationicity
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摘要: 针对高密度饱和盐水钻井液在220 ℃超高温条件下流变性、滤失性能及稳定性难调控问题，以碳纳米管（CNT）为刚性载体，基于含氮阳离子和芳香环与CNT之间的阳离子-π与π-π堆积相互作用，研发了一种高阳离子度两性共聚物包覆CNT低黏降滤失剂CNT/ZPE，并以其作为唯一共聚物降滤失剂，配伍现场常用材料，构建出了一套抗温220 ℃高密度饱和盐水钻井液体系。红外光谱与透射电镜分析结果显示，CNT/ZPE分子结构中含有设计的季铵阳离子、苯环以及磺酸基等结构，高阳离子度两性共聚物成功包覆在了CNT表面。在饱和盐基浆（36%NaCl）与含钙基浆（2%CaCl2）中添加3%CNT/ZPE，220 ℃老化后中压滤失量分别仅为5.4 mL与6.0 mL。1%CNT/ZPE水溶液表观黏度仅5 mPa·s，低于DSP-1、PSP、SO-1等高温深井常用低黏共聚物降滤失剂。构建的饱和盐水钻井液体系的密度在2.0～2.3 g/cm3范围内，经过220 ℃老化16 h、48 h后，各项流变参数合理，高温高压滤失量可控，可抗0.7%CaCl2污染，能满足实际钻井工程需求。该研究还为研发钻井液用碳纳米管基聚合物复合材料提供了新策略。Abstract: High density saturated saltwater drilling fluids at 220 ℃ have rheology, filtration rate and stability that are difficult to control. To address this issue, a low-viscosity fluid loss reducer CNT/ZPE was developed. CNT/ZPE uses carbon nanotube (CNT) as the rigid carrier, and is synthesized through the cation-π and π-π stacking interactions between nitrogen cations/aromatic rings and CNTs. In a CNT/ZPE molecule, the CNT is coated with high cationicity amphoteric copolymer ZPE. Using CNT/ZPE as the sole copolymer fluid loss reducer, a high density saturated saltwater drilling fluid that can be used at temperatures up to 220 ℃ was formulated with other conventional drilling fluid additives. The results of Fourier transform infrared spectroscopy and transmission electron microscopy analyses show that the CNT/ZPE molecules contain the designed quaternary ammonium cations, benzene rings and sulfonic acid groups etc., and the surfaces of CNTs are successfully coated with high cationicity amphoteric copolymer molecules. A salt-saturated base mud (containing 36% NaCl) and a calcium base mud (containing 2% CaCl2) treated with 3% CNT/ZPE have API filtration rate of only 5.4 mL and 6.0 mL after aging at 220 ℃, respectively. The apparent viscosity (AV) of 1% CNT/ZPE water solution is only 5mPa·s, lower than the AVs of the water solutions of other regularly used low-viscosity copolymer fluid loss reducers, such as DSP-1, PSP and SO-1 at the same concentration. The formulated saturated saltwater drilling fluid, at densities between 2.0 g/cm3 and 2.3 g/cm3, have reasonable rheological parameters and controllable high-temperature high-pressure fluid loss after aging at 220 ℃ for 16 hours and 48 hours, respectively. It is resistant to the contamination of 0.7%CaCl2, and is able to satisfy the requirements of field drilling operations. This study also provides a new strategy for developing CNT-based polymer compound materials for use in drilling fluids.
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表 1 CNT/ZPE加量对饱和盐基浆流变参数与滤失量的影响
评价浆 老化
条件AV/
mPa·sPV/
mPa·sYP/
PaFLAPI/
mL4%基浆 老化前 6.5 3.0 3.5 26.0 4%基浆 220 ℃、16 h 5.0 4.0 1.0 35.5 饱和盐基浆
（4%基浆+
36%NaCl）220 ℃、16 h 5.5 3.0 2.5 186.0 饱和盐基浆+
1%CNT/ZPE220 ℃、16 h 5.5 5.0 0.5 32.0 饱和盐基浆+
2%CNT/ZPE220 ℃、16 h 9.5 8.0 1.5 6.8 饱和盐基浆+
3%CNT/ZPE220 ℃、16 h 14.5 13.0 1.5 5.4 
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表 2 CNT/ZPE加量对含钙基浆流变参数与滤失量的影响
评价浆 老化条件 AV/
mPa·sPV/
mPa·sYP/
PaFLAPI/
mL4%基浆 老化前 6.5 3.0 3.5 26.0 4%基浆 220 ℃、16 h 5.0 4.0 1.0 35.5 含钙基浆
（4%基浆+
2%CaCl2）220 ℃、16 h 3.5 2.0 1.5 216.0 含钙基浆+
1%CNT/ZPE220 ℃、16 h 4.0 4.0 0.0 27.0 含钙基浆+
2%CNT/ZPE220 ℃、16 h 7.5 7.0 0.5 9.8 含钙基浆+
3%CNT/ZPE220 ℃、16 h 16.0 14.0 2.0 6.0
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表 3 不同高密度饱和盐水钻井液的流变与滤失性能
ρ/
g·cm−3老化
条件PV/
mPa·sYP/
PaGel/
Pa/PaFLAPI/
mLFLHTHP/
mL开罐
状态2.0 老化前 58 16.5 2.5/10.5 1.8 220 ℃、16 h 52 10.5 2.5/8.0 2.0 8.6 未沉降 220 ℃、48 h 36 8.0 1.5/6.5 2.1 9.6 未沉降 2.2 老化前 78 18.5 3.5/13.5 1.8 220 ℃、16 h 74 13.5 3.5/9.5 2.2 9.0 未沉降 220 ℃、48 h 55 9.5 2.0/8.0 2.4 11.2 未沉降 2.3 老化前 91 19.5 4.0/15.0 2.0 220 ℃、16 h 87 15.5 3.5/10.5 2.8 11.6 未沉降 220 ℃、48 h 67 10.5 2.5/9.0 3.2 13.5 未沉降 注：流变性测试温度60 ℃，FLHTHP测试温度200 ℃、压差3.5 MPa。
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表 4 高密度饱和盐水钻井液体系的抗钙污染性能
CaCl2/
%老化
条件PV/
mPa·sYP/
PaGel/
Pa/PaFLAPI/
mLFLHTHP/
mL开罐
状态0.5 老化前 53 14.5 1.5/7.5 2.2 220 ℃、16 h 46 13.0 3.5/9.5 2.8 11.8 未沉降 0.7 老化前 50 14.0 1.5/7.0 2.5 220 ℃、16 h 42 15.5 4.0/11.5 3.4 14.5 未沉降 注：流变性测试温度60 ℃，FLHTHP测试温度200 ℃、压差3.5 MPa。
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