纳米复合凝胶自降解暂堵剂制备及性能评价

doi:10.3969/j.issn.2096-1693.2025.02.005

摘要/Abstract

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。

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

中图分类号:

金辉. 纳米复合凝胶自降解暂堵剂制备及性能评价[J]. 石油科学通报, 2025, 10(3): 590-602.

JIN Hui. Preparation and performance evaluation of composite nano gel self-degrading temporary plugging agent[J]. Petroleum Science Bulletin, 2025, 10(3): 590-602.

https://sykxtb.cup.edu.cn/CN/Y2025/V10/I3/590

图/表 17

图1 PAE型暂堵剂合成示意图及其反应方程式

Fig. 1 Schematic diagram of the synthesis of PAE-type temporary plugging agent and its reaction equation

图2 岩心封堵性能实验示意图

Fig. 2 Schematic diagram of core blocking performance experiments

表1 暂堵剂强度代码^[31-33]

Table 1 The code of temporary plugging agent strength^[31-33]

暂堵剂强度	状态描述
1	凝胶看起来与原始聚合物溶液具有相同的黏度
2	凝胶看起来比初始聚合物溶液略稠
3	大多数凝胶在颠倒时通过重力流入瓶盖
4	只有部分凝胶不容易在颠倒时通过重力流入瓶盖
5	在颠倒瓶子时，凝胶不会流入瓶盖
6	凝胶不会通过重力流入瓶盖
7	凝胶在重力作用下，在流向瓶盖的中途变形
8	在颠倒瓶子时，凝胶表面仅轻微变形
9	在颠倒瓶子时，凝胶表面没有发生变形

图3 单体浓度对暂堵剂性能的影响

Fig. 3 Influence of monomer concentration on performance of temporary plugging agent

图4 不同APS加量下的暂堵剂成胶时间及凝胶强度

Fig. 4 Gel formation time and gel strength of temporary plugging agent under different APS dosage

图5 温度对暂堵剂凝胶时间及凝胶强度的影响

Fig. 5 Influence of temperature on gel time and gel strength of temporary plugging agent

图6 疏水单体对暂堵剂性能的影响

Fig. 6 Influence of hydrophobic monomer on performance of temporary plugging agent

图7 暂堵剂PAE与降解后的红外光谱图

Fig. 7 The infrared spectra of PAE and its degradation products

图8 PAE型暂堵剂热重曲线

Fig. 8 Thermogravimetric curve of PAE temporary plugging agent

图9 暂堵剂扫描显微镜图

Fig. 9 Scanning microscope of temporary plugging agent

图10 温度对暂堵剂降解性能的影响

Fig. 10 Effect of temperature on degradation performance of temporary plugging agent

图11 pH值对暂堵剂降解性能的影响

Fig. 11 Effect of pH value on degradation performance of temporary plugging agent

图12 矿化度对暂堵剂降解性能的影响

Fig. 12 Effect of salinity on degradation performance of temporary plugging agent

图13 (a) PAE暂堵剂与普通暂堵剂降解效率对比(b) 暂堵剂降解对比实验(A为普通暂堵剂，B为PAE型暂堵剂)

Fig. 13 (a) The comparison of degradation efficiency between PAE and ordinary plugging agent (b) The degradation experiments of temporary plugging agent (A is ordinary plugging agent, B is PAE type plugging agent)

图14 (a) 不同交联度PAE暂堵剂的封堵率和突破压力(b)普通暂堵剂和PAE暂堵剂自降解突破压力对比

Fig. 14 (a) The plugging rate and breakthrough pressure of PAE temporary plugging agent with different cross-linking percent (b) The comparison of breakthrough pressure of self-degradation between normal and PAE temporary plugging agents

表2 暂堵剂成胶与破胶后的岩心渗透率恢复率

Table 2 Core recovery rates after cementing and breaking of temporary plugging agent

岩心编号	岩心渗透率K/(10^-3 μm²)	恢复后渗透率K₂/(10^-3 μm²)	渗透率恢复值/%
1	1596.4	1477.7	92.56
2	1965.2	1855.3	94.41
3	2139.9	2001.5	93.53

图15 自降解暂堵剂成胶与降解机理

Fig. 15 Self-degradable temporary plugging agent gel formation and degradation mechanism

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