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纳米复合凝胶自降解暂堵剂制备及性能评价
金辉
大庆油田有限责任公司第七采油厂,大庆 163517
Preparation and performance evaluation of composite nano gel self-degrading temporary plugging agent
JIN Hui
No.7 Oil Production Plant, Daqing Oilfield Co., Ltd., Daqing 163517, China

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摘要  针对油气田开发中传统暂堵剂在封堵后期破胶困难、降解时间长、成胶强度低及残留物对地层渗透率损伤大等问题,本研究通过物理化学交联策略,设计并合成了一种基于纳米复合材料的自降解凝胶暂堵剂(PAE)。通过水溶液自由基聚合法,将丙烯酰胺(AM)、丙烯酸(AA)、聚乙二醇二丙烯酸酯(AE)与疏水单体甲基丙烯酸十八烷基酯(SMA)共聚,并引入纳米二氧化硅(SiO2)增强交联网络。系统探究了交联剂(MBA)、疏水单体含量、引发剂(APS)浓度及温度对凝胶时间与强度的影响规律,揭示了温度(70~120 ℃)、pH(3~12)及矿化度 (20~50 g/L)对PAE降解行为的调控机制。通过扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)和热重分析(TGA) 表征了PAE的微观形貌、化学结构与热稳定性。实验结果表明:在优化条件下(单体浓度 8%、APS 0.2%、SMA 0.4%、温度 70 ℃),PAE成胶时间为 30~120 min,形成致密三维网络结构,凝胶强度达 9 级(颠倒无变形);其在 70~120 ℃环境中的降解时间为 3~10 h,降解后粘度低于 10 mPa·s,显著优于传统暂堵剂(>96 h)。填砂管实验显示,PAE突破压力梯度为 1.870 MPa/m,封堵率>90%;岩心驱替实验表明,破胶后渗透率恢复率>90%,验证了其对地层的低伤害特性。机理分析表明,PAE的高强度封堵源于物理—化学双交联网络与纳米SiO2 的协同增强作用,而自降解行为则通过碱性条件下酯键皂化与疏水缔合网络解离实现。本研究为油田高效环保型暂堵剂的开发提供了理论支撑与技术方案。
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关键词 : 纳米材料,不稳定交联剂,疏水单体,复合材料,聚合物,凝胶
Abstract

To address the challenges of conventional temporary plugging agents in oilfield development, such as inefficient gel breaking at later stages, prolonged degradation time, low gel strength, and significant permeability damage caused by residues, this study developed a self-degrading nano-composite gel temporary plugging agent (PAE) based on a physicochemical cross-linking strategy. The PAE was synthesized via free radical polymerization in aqueous solution using acrylamide (AM), acrylic acid (AA), polyethylene glycol diacrylate (AE), and hydrophobic monomer stearyl methacrylate (SMA), with nano-silica (SiO₂) incorporated to reinforce the cross-linked network. The effects of cross-linker (MBA) dosage, hydrophobic monomer content, initiator (APS) concentration, and temperature on gelation time and strength were systematically investigated. The degradation behavior of PAE under varying temperatures (70-120 ℃), pH (3-12), and salinity (20-50 g/L) was elucidated. Characterization techniques including Scanning Electron Microscopy (SEM), Fourier-Transform Infrared Spectroscopy (FTIR), and Thermogravimetric Analysis (TGA) were employed to analyze the microstructure, chemical composition, and thermal stability of PAE. Experimental results demonstrated that under the optimized conditions (monomer concentration 8%, APS 0.2%, SMA 0.4%, and temperature 70 ℃), PAE exhibited controllable gelation time (30-120 min) and formed a dense three-dimensional network with a gel strength of grade 9 (no deformation upon inversion). The degradation time of PAE ranged from 3 to 10 h at 70- 120 ℃, with post-degradation viscosity below 10 mPa·s, significantly outperforming conventional agents (>96 h). Sand-packed tube tests revealed a breakthrough pressure gradient of 1.870 MPa/m and a plugging efficiency exceeding 90%. Core flooding experiments confirmed a permeability recovery rate above 90% after gel breaking, indicating minimal formation damage. Mechanistic studies revealed that the high plugging strength of PAE originated from the synergistic enhancement of physicochemical dual-crosslinking networks and nano-SiO2, while self-degradation was achieved through ester bond saponification under alkaline conditions and dissociation of hydrophobic association networks. This research provides a theoretical foundation and technical solution for developing high-performance, environmentally friendly temporary plugging agents in oilfield applications

Key words: nanomaterials; unstable crosslinkers; hydrophobic monomers; composites; polymer; gel
收稿日期: 2025-06-13     
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通讯作者: jinhuicq@petrochina.com.cn
引用本文:   
金辉. 纳米复合凝胶自降解暂堵剂制备及性能评价. 石油科学通报, 2025, 10(03): 590-602 JIN Hui. Preparation and performance evaluation of composite nano gel self-degrading temporary plugging agent. Petroleum Science Bulletin, 2025, 10(03): 590-602.
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