Supramolecular fracturing fluids: Mechanism of action and research progress

doi:10.16085/j.issn.1000-6613.2023-1504

Abstract

Abstract:

Supramolecular fracturing fluid is a self-assembled fracturing fluid system based on non-covalent bond, which has the characteristics of reversible shear, adaptive, low damage and so on. It is a hot field in the research of new adaptive fracturing fluids, but there are many problems such as poor temperature and salt resistance, harsh operating conditions and high cost. This paper introduced the intermolecular interaction and regulation mechanism of supramolecular fracturing fluids based on hydrophobic association, hydrogen bonding, electrostatic interaction and host-guest interaction. It was systematically reviewed the design and synthesis of polymers, surfactants and other self-assembled elements, and its research progress in supramolecular fracturing fluids. There were compared and analyzed with the advantages and disadvantages of different kinds of supramolecular fracturing fluids. According to the principle of supramolecular interaction, the design and synthesis of new high performance and low cost self-assembly elements were the core of supramolecular fracturing fluid research. It was the key to the development of supramolecular fracturing fluid to regulate the self-assembly of supramolecular system by the synergistic interaction of multiple non-covalent bonds. The next step was to develop new adaptive supramolecular fracturing fluids that can meet harsh reservoir conditions.

Key words: supramolecular fracturing fluid, non-covalent bond interaction, research progress, oil and gas field development

摘要：

超分子压裂液是一种基于非共价键作用的自组装压裂液体系，具有剪切可逆、自适应、低伤害等特点，是新型自适应压裂液研究的热点领域，但普遍存在耐温耐盐性能差、使用条件苛刻、成本高等问题。本文介绍了基于疏水缔合、氢键、静电相互作用、主客体包合作用等超分子压裂液的分子间作用及调控机理，系统综述了聚合物、表面活性剂等自组装基元设计合成及其在超分子压裂液方面的研究进展，对比分析了不同种类超分子压裂液优势和不足。根据超分子作用原理设计合成新型高性能、低成本的自组装基元是超分子压裂液研究的核心，利用多重非共价键协同相互作用调控超分子体系自组装是超分子压裂液研发的关键，研发新型可满足苛刻储层条件的自适应超分子压裂液是下一步的攻关方向。

关键词: 超分子压裂液, 非共价键作用, 研究进展, 油气田开发

CLC Number:

TQ317

WANG Jinran, WU Junwen, YIN Junrong, XIAN Chenggang, JIA Wenfeng. Supramolecular fracturing fluids: Mechanism of action and research progress[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5555-5568.

王金冉, 武俊文, 殷俊荣, 鲜成钢, 贾文峰. 超分子压裂液：作用机理及研究进展[J]. 化工进展, 2024, 43(10): 5555-5568.

Figures/Tables 14

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类型	性能及应用	参考文献
疏水缔合聚合物（HMP）与阳离子表面活性剂（VES）协同	黏弹性和悬浮能力高，返排率高，破胶后残渣含量少，对储层伤害性降低至50%，导电性92%，可适用于苏里格盆地	[27]
疏水缔合聚合物与阴离子表面活性剂十二烷基苯磺酸钠（SDBS）协同	黏弹性、耐温耐盐性好，剪切可逆，破胶后几乎无残渣，可适用于油藏	[28]
疏水缔合聚合物（HMP）与两性表面活性剂（OA16）协同	具有物理交联型和化学交联型压裂液的清洁性、黏弹性和耐温耐剪切性优势，在90℃下能保持较高的黏弹性，适应性强	[5]
疏水改性聚丙烯酰胺与双子表面活性剂 1, 2-N,N-双(二甲基十八烷基)乙烯溴化铵协同	耐剪切性好，对储层伤害性低，适应温度比单体的双子表面活性剂高30℃，有希望适用于耐高温清洁压裂液	[29]

类型	性能及应用	参考文献
疏水缔合聚合物（HMP）与阳离子表面活性剂（VES）协同	黏弹性和悬浮能力高，返排率高，破胶后残渣含量少，对储层伤害性降低至50%，导电性92%，可适用于苏里格盆地	[27]
疏水缔合聚合物与阴离子表面活性剂十二烷基苯磺酸钠（SDBS）协同	黏弹性、耐温耐盐性好，剪切可逆，破胶后几乎无残渣，可适用于油藏	[28]
疏水缔合聚合物（HMP）与两性表面活性剂（OA16）协同	具有物理交联型和化学交联型压裂液的清洁性、黏弹性和耐温耐剪切性优势，在90℃下能保持较高的黏弹性，适应性强	[5]
疏水改性聚丙烯酰胺与双子表面活性剂 1, 2-N,N-双(二甲基十八烷基)乙烯溴化铵协同	耐剪切性好，对储层伤害性低，适应温度比单体的双子表面活性剂高30℃，有希望适用于耐高温清洁压裂液	[29]

途径	原料	性能	参考文献
带有相反电荷的聚阴离子和聚阳离子通过库仑力形成具有动态网络的新型压裂液	阳离子聚合物CP与阴离子聚合物AP	具有良好的黏弹性、耐高温性、抗剪切性，在130℃、170s^-1下，溶液的黏度保持在40mPa·s以上，破胶后几乎无残渣，对储层损伤小	[36]
合成的两性离子聚合物	阴离子单体4-苯乙烯磺酸钠（SSS）、阳离子单体N,N-二甲基十八烷基烯丙基氯化铵（DOAC）、丙烯酰胺（AM）等	具有优异的耐盐、耐高温、耐剪切性，在140℃、170s^-1条件下，0.5%（质量分数，下同）的聚合物溶液黏度保持在92mPa·s以上；当盐质量分数为10.0%时，0.3%的聚合物表观黏度保持在948mPa·s左右	[37]
利用带相反电荷的表面活性剂通过静电相互作用构建的超分子聚集体	阴离子/阳离子-非离子表面活性剂（GAES-9）与十六烷基三甲基溴化铵（CTAB）	总浓度为200mg·L^-1复合体系在10⁵mg·L^-1盐溶液浓度下仍具有良好的耐盐性，可适用于低渗透油藏	[38]
利用带相反电荷的表面活性剂通过静电相互作用构建的超分子聚集体	阳离子表面活性剂CAS与阴离子聚丙烯酰胺SPAM	具有良好的黏弹性、耐高温性，在90℃下，二者的混合物SP的表观黏度随表面活性剂浓度的增加而增加或保持不变	[39]

途径	原料	性能	参考文献
带有相反电荷的聚阴离子和聚阳离子通过库仑力形成具有动态网络的新型压裂液	阳离子聚合物CP与阴离子聚合物AP	具有良好的黏弹性、耐高温性、抗剪切性，在130℃、170s^-1下，溶液的黏度保持在40mPa·s以上，破胶后几乎无残渣，对储层损伤小	[36]
合成的两性离子聚合物	阴离子单体4-苯乙烯磺酸钠（SSS）、阳离子单体N,N-二甲基十八烷基烯丙基氯化铵（DOAC）、丙烯酰胺（AM）等	具有优异的耐盐、耐高温、耐剪切性，在140℃、170s^-1条件下，0.5%（质量分数，下同）的聚合物溶液黏度保持在92mPa·s以上；当盐质量分数为10.0%时，0.3%的聚合物表观黏度保持在948mPa·s左右	[37]
利用带相反电荷的表面活性剂通过静电相互作用构建的超分子聚集体	阴离子/阳离子-非离子表面活性剂（GAES-9）与十六烷基三甲基溴化铵（CTAB）	总浓度为200mg·L^-1复合体系在10⁵mg·L^-1盐溶液浓度下仍具有良好的耐盐性，可适用于低渗透油藏	[38]
利用带相反电荷的表面活性剂通过静电相互作用构建的超分子聚集体	阳离子表面活性剂CAS与阴离子聚丙烯酰胺SPAM	具有良好的黏弹性、耐高温性，在90℃下，二者的混合物SP的表观黏度随表面活性剂浓度的增加而增加或保持不变	[39]

压裂液名称	非共价键作用	参考文献
超分子自组装	主客体包合作用、氢键、疏水缔合作用	[58]
超分子VES清洁压裂液	氢键、疏水缔合作用	[8]
表面活性剂类聚合物	氢键、静电相互作用	[59]
超分子压裂液NAF	主客体包合作用、疏水缔合作用	[31]
超分子聚合物清洁CO₂压裂液	氢键、疏水缔合作用	[60]
超分子表面活性剂压裂液	疏水缔合作用	[61]
超分子聚合物压裂液	氢键、疏水缔合作用、静电相互作用	[62]
超分子黏弹性聚合物基压裂液	疏水缔合作用、主客体包合作用	[63]