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用于高温碳酸盐岩储层酸化的缓凝冻胶酸：缓凝性能及机理研究

Retarded Gelled Acid for High-Temperature Carbonate Reservoir Acidizing: Retardancy and Mechanism Study.

作者信息

Chen Weihua, Liu Pingli, Li Li, Wang Hancheng, Du Juan, Jia Yucheng, Chen Xiang, Gu Haoran

机构信息

Engineering Technology Research Institute, PetroChina Southwest Oil and Gas Field Company, Chengdu, Sichuan 610017, China.

State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, Sichuan 610500, China.

出版信息

ACS Omega. 2025 Mar 18;10(12):12441-12452. doi: 10.1021/acsomega.4c11617. eCollection 2025 Apr 1.

DOI:10.1021/acsomega.4c11617
PMID:40191308
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11966580/
Abstract

Carbonate reservoirs, characterized by deep burial, high temperatures, strong heterogeneity, and extensive fracturing, pose challenges for effective acidizing stimulation. Gelled acid treatment offers a solution to issues such as severe acid fluid loss and limited penetration in high-temperature carbonate reservoirs. However, current gelled acids often lack sufficient temperature resistance, and the retardation effect of single gelled acids remains limited. In this study, a temperature-resistant gelled agent was synthesized using acrylamide (AM), methacryloyloxyethyl dimethyl octadecyl ammonium bromide (DM-18), dimethyl diallyl ammonium chloride (DMDAAC), and 2-acrylamido-2-methylpropanesulfonic acid (AMPS), achieving the designed molecular structure. Additionally, the zwitterionic surfactant dodecyl betaine (BS-12) was selected as a retardation synergist, forming a retarded gelled acid with excellent stimulation performance and effective rock etching. Static retardation rate tests and high-temperature, high-pressure acid-rock reaction kinetic experiments were conducted to compare the retardation effects of gelled acid and retarded gelled acid. The kinetics equations and activation energies for hydrochloric acid, gelled acid, and retarded gelled acid under varying temperatures and concentrations were determined. Results demonstrated that the retarded gelled acid exhibited superior retardation efficiency compared to single gelled acid, achieving a retardation rate exceeding 80% within 1 h. Its kinetic reaction rate and activation energy at high temperatures were lower than those of single gelled acid, highlighting its stability and effectiveness in high-temperature environments. Scanning electron microscopy and infrared spectroscopy analyses revealed the retardation mechanism: the polymer network hindered hydrogen ion transfer, while the adsorption film prevented direct contact between hydrogen ions and the rock surface.

摘要

碳酸盐岩储层具有埋藏深、温度高、非均质性强和裂缝发育等特点，给有效的酸化增产措施带来了挑战。胶凝酸处理为高温碳酸盐岩储层中酸液严重漏失和穿透有限等问题提供了解决方案。然而，目前的胶凝酸往往缺乏足够的耐温性，单一胶凝酸的缓速效果仍然有限。在本研究中，使用丙烯酰胺（AM）、甲基丙烯酰氧乙基二甲基十八烷基溴化铵（DM - 18）、二甲基二烯丙基氯化铵（DMDAAC）和2 - 丙烯酰胺基 - 2 - 甲基丙磺酸（AMPS）合成了一种耐温胶凝剂，实现了设计的分子结构。此外，选择两性离子表面活性剂十二烷基甜菜碱（BS - 12）作为缓速增效剂，形成了具有优异增产性能和有效刻蚀岩石能力的缓速胶凝酸。进行了静态缓速率测试以及高温高压酸岩反应动力学实验，以比较胶凝酸和缓速胶凝酸的缓速效果。确定了不同温度和浓度下盐酸、胶凝酸和缓速胶凝酸的动力学方程和活化能。结果表明，与单一胶凝酸相比，缓速胶凝酸表现出优异的缓速效率，在1小时内缓速率超过80%。其在高温下的动力学反应速率和活化能低于单一胶凝酸，突出了其在高温环境下的稳定性和有效性。扫描电子显微镜和红外光谱分析揭示了缓速机理：聚合物网络阻碍了氢离子传递，而吸附膜阻止了氢离子与岩石表面的直接接触。

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