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海藻酸盐包覆的温度敏感型聚合物凝胶微球的合成与性能评价

Synthesis and Performance Evaluation of Alginate-Coated Temperature-Sensitive Polymer Gel Microspheres.

作者信息

Song Zhaozheng, Hu Junhang, Liu Ping, Sun Yili

机构信息

State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Beijing 102206, China.

Research and Development Center for the Sustainable Development of Continental Sandstone Mature Oilfield by National Energy Administration, Beijing 102206, China.

出版信息

Gels. 2023 Jun 12;9(6):480. doi: 10.3390/gels9060480.

DOI:10.3390/gels9060480
PMID:37367150
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10297886/
Abstract

With the long-term water-flooding development of the reservoir, the non-homogeneity of the formation is increasing and the reservoir environment is deteriorating; the microspheres used for deep plugging have shown disadvantages, such as poor temperature and salt resistance and faster expansion. In this study, a polymeric microsphere was synthesized that is resistant to high temperature and high salt and can achieve slow expansion and slow release for deep migration. P(AA-AM-SA)@TiO polymer gel/inorganic nanoparticle microspheres were prepared by reversed-phase microemulsion polymerization using acrylamide (AM) and acrylic acid (AA) as monomers, 3-methacryloxypropyltrimethoxysilane (KH-570)-modified TiO as the inorganic core, and sodium alginate (SA) as a temperature-sensitive coating material. Through single-factor analysis of the polymerization process, the optimal synthesis conditions were determined as follows: the oil(Cyclohexane)-water volume ratio was 8:5, the emulsifier mass ratio (Span-80:Tween-80) was 3:1 (10 wt% of the total system amount), the stirring speed was 400 r/min, the reaction temperature was 60 °C, and the initiator (ammonium persulfate and sodium bisulfite) dosage was 0.6 wt%. The size of the dried polymer gel/inorganic nanoparticle microspheres prepared by the optimized synthesis conditions was 10~40 μm with uniform particle size. The observation of P(AA-AM-SA)@TiO microspheres reveals that the Ca elements are uniformly distributed on the microspheres, and FT-IR indicates that the synthesized product is the target product. TGA shows that the polymer gel/inorganic nanoparticle microspheres have better thermal stability after the addition of TiO, with a larger mass loss at 390 °C, which can adapt to the medium-high permeability reservoir environment. The thermal and aqueous salinity resistance of the P(AA-AM-SA)@TiO microspheres was tested, and the cracking temperature of P(AA-AM-SA)@TiO microsphere temperature-sensitive material was 90 °C. It still has favorable water absorption and swelling performance under the sodium salt concentration of 2.5 × 10 mg/L and can tolerate calcium salt up to 2.0 × 10 mg/L. Plugging Performance Test results show that the microspheres have good injectability between the permeability of 1.23 and 2.35 μm and good plugging effect near the permeability of 2.20 μm. At high temperature and high salinity, P(AA-AM-SA)@TiO microspheres have a remarkable effect on profile control and water shutoff, the plugging rate reaches 95.3%, and the oil recovery rate is increased by 12.89% compared with water flooding, achieving the effect of slow swelling and slow release.

摘要

随着油藏长期注水开发,地层非均质性不断增强,油藏环境日益恶化;用于深部封堵的微球出现了耐温耐盐性差、膨胀速度快等缺点。本研究合成了一种耐高温、耐高盐且能实现深部运移缓慢膨胀、缓慢释放的聚合物微球。以丙烯酰胺(AM)和丙烯酸(AA)为单体,3-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)改性的TiO为无机核,海藻酸钠(SA)为温敏包覆材料,通过反相微乳液聚合法制备了P(AA-AM-SA)@TiO聚合物凝胶/无机纳米颗粒微球。通过对聚合过程进行单因素分析,确定最佳合成条件如下:油(环己烷)-水体积比为8:5,乳化剂质量比(Span-80:Tween-80)为3:1(占体系总量的10 wt%),搅拌速度为400 r/min,反应温度为60℃,引发剂(过硫酸铵和亚硫酸氢钠)用量为0.6 wt%。优化合成条件制备的干燥聚合物凝胶/无机纳米颗粒微球粒径为1040μm,粒径均匀。对P(AA-AM-SA)@TiO微球的观察表明,Ca元素均匀分布在微球上,傅里叶变换红外光谱(FT-IR)表明合成产物为目标产物。热重分析(TGA)表明,添加TiO后聚合物凝胶/无机纳米颗粒微球具有较好的热稳定性,在390℃时质量损失较大,能够适应中高渗透油藏环境。测试了P(AA-AM-SA)@TiO微球的抗温抗盐性能,P(AA-AM-SA)@TiO微球温敏材料的开裂温度为90℃。在钠盐浓度为2.5×10 mg/L时仍具有良好吸水溶胀性能,耐钙盐能力可达2.0×10 mg/L。封堵性能测试结果表明,微球在渗透率为1.232.35μm之间具有良好的注入性,在渗透率为2.20μm附近封堵效果良好。在高温高盐条件下,P(AA-AM-SA)@TiO微球调剖堵水效果显著,封堵率达到95.3%,与水驱相比采收率提高了12.89%,实现了缓慢溶胀、缓慢释放的效果。

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