疏水材料在油田化学领域研究进展与展望

doi:10.16085/j.issn.1000-6613.2023-1939

化工进展 ›› 2024, Vol. 43 ›› Issue (11): 6293-6309.DOI: 10.16085/j.issn.1000-6613.2023-1939

• 材料科学与技术 • 上一篇

疏水材料在油田化学领域研究进展与展望

章超¹(), 孙金声¹(), 吕开河¹, 黄贤斌¹, 戴嘉君¹, 李茂², 姚如钢³

^1.中国石油大学（华东）石油工程学院，山东青岛 266580
^2.中国石油集团西部钻探工程有限公司工程技术研究院，新疆克拉玛依 834000
^3.中国石油集团长城钻探工程有限公司钻井液公司，辽宁盘锦 124010

收稿日期:2023-11-03 修回日期:2023-12-25 出版日期:2024-11-15 发布日期:2024-12-07
通讯作者: 孙金声
作者简介:章超（1995—），男，博士研究生，研究方向为钻井液材料研发。E-mail：2249149267@qq.com。
基金资助:
山东省重点研发计划院士团队支持项目(2020ZLYS07)

Research progress and prospects of hydrophobic materials in oilfield chemistry

ZHANG Chao¹(), SUN Jinsheng¹(), LYU Kaihe¹, HUANG Xianbin¹, DAI Jiajun¹, LI Mao², YAO Rugang³

^1.College of Petroleum Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China
^2.Engineering Technology Research Institute, China National Petroleum Corporation West Drilling Engineering Company Limited, Karamay 834000, Xinjiang, China
^3.Drilling Fluid Branch, China National Petroleum Corporation Great Wall Drilling Company Limited, Panjin 124010, Liaoning, China

Received:2023-11-03 Revised:2023-12-25 Online:2024-11-15 Published:2024-12-07
Contact: SUN Jinsheng

摘要/Abstract

摘要：

在油田化学领域，通过研选合适的疏水材料对井壁或储层岩石表面进行润湿性改造，可以减弱表面对水相的亲和性，从而达到抑制岩石水化、减少储层水相圈闭及改善储层油气渗流能力等目的，极大提高油气田的开发效益。本文简要介绍了疏水材料的种类并分析了疏水材料形成憎水性表面的原理，重点从稳定井壁、保护储层、提高油气采收率和改善乳液及泡沫稳定性四个关键方面阐述了疏水材料在油田化学领域中的研究进展。针对于目前存在的不足，展望了疏水材料作为一种油田化学助剂，未来应向着低成本、强配伍、多功能、环境友好型方向发展，以满足其在油田化学领域中不断增长的需求。

关键词: 疏水材料, 水亲和性, 润湿性改造, 疏水原理, 油田化学

Abstract:

In the field of oilfield chemistry, the application of hydrophobic materials has achieved remarkable results. The wettability modification of the wellbore wall or reservoir rock surface by suitable hydrophobic materials can weaken the affinity of the surface for the aqueous phase. This method can effectively inhibit the hydration of rocks, reduce the aqueous phase trapping of reservoirs and improve the seepage capacity of oil and gas in the reservoirs, which greatly improves the development benefits of oil and gas fields. In this paper, the types of hydrophobic materials were briefly introduced and the mechanism of hydrophobic materials to form hydrophobic surfaces was analyzed. The research progress of hydrophobic materials in the field of oilfield chemistry was described from four essential aspects: stabilizing the wellbore, protecting the reservoir, enhancing oil and gas recovery, and improving the stability of emulsions and foams. Given the current deficiencies of hydrophobic materials as a kind of oilfield chemical additives, the future development of hydrophobic materials should be toward the direction of low cost, strong compatibility, multi-functionality and environment-friendly to achieve the increasing demand in the field of oilfield chemistry.

Key words: hydrophobic materials, hydrophilic property, wettability modification, hydrophobic mechanism, oilfield chemistry

中图分类号:

TE39

章超, 孙金声, 吕开河, 黄贤斌, 戴嘉君, 李茂, 姚如钢. 疏水材料在油田化学领域研究进展与展望[J]. 化工进展, 2024, 43(11): 6293-6309.

ZHANG Chao, SUN Jinsheng, LYU Kaihe, HUANG Xianbin, DAI Jiajun, LI Mao, YAO Rugang. Research progress and prospects of hydrophobic materials in oilfield chemistry[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6293-6309.

图/表 21

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类别	结构/组成	代表物质	产生低表面能效应原理	成本及表面能对比
有机氟（短链）	短碳链化合物，氢部分或全部被氟替代	氟甲烷CH₃F、四氟化碳CF₄	F原子电负性高，形成弱极性C－F键	成本高，降低表面能效果优
有机硅	硅原子与碳基团结合，形成硅-碳键	二甲基硅烷(CH₃)₂SiH₂、乙基甲基硅氧烷CH₃Si(O)C₂H₅	有机基团降低分子间作用力，Si－O键稳定	成本较高，降低表面能效果较优
长烷基链化合物	长直链或支链饱和碳氢化合物	十二烷、硬脂酸	长链定向减张力，低能界面稳定	成本最低，降低表面能效果最差
氟化硅氧烷	硅氧烷结构，部分氢被氟替代	三氟丙基甲基硅氧烷、全氟烷氧基硅氧烷	结合了有机氟侧链疏水性和硅氧链稳定性	成本最高，降低表面能效果最优
长链含氟烷基化合物	长碳链，部分碳原子氢被氟替代	全氟辛烷磺酸、全氟十二烷酸	C－F键比C－H键更稳定，形成的低能界面更稳定	成本最高，降低表面能效果最优

类别	结构/组成	代表物质	产生低表面能效应原理	成本及表面能对比
有机氟（短链）	短碳链化合物，氢部分或全部被氟替代	氟甲烷CH₃F、四氟化碳CF₄	F原子电负性高，形成弱极性C－F键	成本高，降低表面能效果优
有机硅	硅原子与碳基团结合，形成硅-碳键	二甲基硅烷(CH₃)₂SiH₂、乙基甲基硅氧烷CH₃Si(O)C₂H₅	有机基团降低分子间作用力，Si－O键稳定	成本较高，降低表面能效果较优
长烷基链化合物	长直链或支链饱和碳氢化合物	十二烷、硬脂酸	长链定向减张力，低能界面稳定	成本最低，降低表面能效果最差
氟化硅氧烷	硅氧烷结构，部分氢被氟替代	三氟丙基甲基硅氧烷、全氟烷氧基硅氧烷	结合了有机氟侧链疏水性和硅氧链稳定性	成本最高，降低表面能效果最优
长链含氟烷基化合物	长碳链，部分碳原子氢被氟替代	全氟辛烷磺酸、全氟十二烷酸	C－F键比C－H键更稳定，形成的低能界面更稳定	成本最高，降低表面能效果最优

类别	疏水原理	表面水分布形态
Young模型^[27]	研究了液体在光滑基材表面的润湿性，描述固气、固液、液气界面张力γ_sg、γ_sl、γ_lg与接触角θ之间的关系，即γ_sg-γ_sl=γ_lgcosθ
Wenzel模型^[28]	研究了液体在粗糙基材表面的润湿性，水相对表面凹槽的填充增大了水相的接触面积，若材料表面亲水，粗糙结构会增强表面的亲水性，反之，则更加疏水
Cassie模型^[29]	对Wenzel模型进一步研究，提出了复合接触理论^[30]，气相填充凹槽，液相无法浸润，微观上表现为液相对固气复合表面的浸润
亚稳态模型^[31]	基于能量势垒原则，外部干扰导致固液间气相不稳，水相浸润，呈现从Cassie到Wenzel的亚稳态
荷叶态模型	荷叶表面含蜡状物质，产生自清洁的关键是表面结构，微米级乳突和纳米级小纤毛，能锁住空气、托起水滴，阻隔浸润
壁虎态模型	壁虎脚掌表面有大量微米级刚毛和纳米级毛状物，形成密封和开放气囊，密封气囊与大气间的压差可产生强黏附力，开放气囊可提高表面疏水性，赋予壁虎强黏附性和超疏水性^[32]

类别	疏水原理	表面水分布形态
Young模型^[27]	研究了液体在光滑基材表面的润湿性，描述固气、固液、液气界面张力γ_sg、γ_sl、γ_lg与接触角θ之间的关系，即γ_sg-γ_sl=γ_lgcosθ
Wenzel模型^[28]	研究了液体在粗糙基材表面的润湿性，水相对表面凹槽的填充增大了水相的接触面积，若材料表面亲水，粗糙结构会增强表面的亲水性，反之，则更加疏水
Cassie模型^[29]	对Wenzel模型进一步研究，提出了复合接触理论^[30]，气相填充凹槽，液相无法浸润，微观上表现为液相对固气复合表面的浸润
亚稳态模型^[31]	基于能量势垒原则，外部干扰导致固液间气相不稳，水相浸润，呈现从Cassie到Wenzel的亚稳态
荷叶态模型	荷叶表面含蜡状物质，产生自清洁的关键是表面结构，微米级乳突和纳米级小纤毛，能锁住空气、托起水滴，阻隔浸润
壁虎态模型	壁虎脚掌表面有大量微米级刚毛和纳米级毛状物，形成密封和开放气囊，密封气囊与大气间的压差可产生强黏附力，开放气囊可提高表面疏水性，赋予壁虎强黏附性和超疏水性^[32]

体系配方	条件	AV/mPa·s	PV/mPa·s	YP/Pa	FL_API/mL	FL_HTHP/mL
配方+50g/L 10μm碳酸钙	老化前	37.5	16.0	21.5	3.8	—
配方+50g/L 10μm碳酸钙	150℃老化16h后	15.0	14.0	1.0	22.0	31.0
配方+50g/L 10μm碳酸钙（STG）	老化前	58.0	34.0	24.0	6.4	—
配方+50g/L 10μm碳酸钙（STG）	150℃老化16h后	20.5	17.0	3.5	3.8	12.0

疏水材料在油田化学领域研究进展与展望

Research progress and prospects of hydrophobic materials in oilfield chemistry

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