Synthesis and Performance Evaluation of a High-Temperature Resistant Long-Acting Self-Generated Acid Fluid System
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摘要: 针对深层高温碳酸盐岩储层酸化改造中，常规酸液反应过快而现有自生酸生酸强度低、耐温性不足的问题，研发了一种新型耐高温生酸剂SFACA，并据此构建了耐高温长效自生酸酸液体系。实验结果表明，SFACA基于“活化-水解-解离-循环催化”的高效生酸机制，可在60 ℃～180 ℃温度范围内持续释放离子，并在140 ℃以上激发高效生酸活性，有效氢离子浓度可达7.8 mol·kg−1，且通过优化剂/水质量比可实现酸浓度的灵活调控。基于SFACA所构建的自生酸酸液体系配伍性良好，对碳酸盐岩主矿物CaCO3表现出高效溶蚀能力，在160 ℃和180 ℃下的酸岩有效作用时间分别达7 h和4 h，酸岩反应速率分别为1.45×10−7 mol·cm−2·s−1和2.46×10−7 mol·cm−2·s−1，具备长效作用特性。此外，该酸液在160 ℃和180 ℃下对N80钢片的动态腐蚀速率分别为56.3 g·m−2·h−1和67.8 g·m−2·h−1，具有良好的缓蚀性能。该自生酸酸液体系实现了高温条件下的高酸度、长效缓释与高效溶蚀，能够为160 ℃～180 ℃深层高温碳酸盐岩储层的高效改造提供可靠的技术支撑。Abstract: In response to the challenges in acidizing deep high-temperature carbonate reservoirs, where conventional acids react too rapidly and existing self-generated acids suffer from insufficient acid-generated capacity and poor temperature resistance, this study developed a novel high-temperature resistant acid-generated agent, SFACA, and constructed a high-temperature long-lasting self-generated acid system based on it. Experimental results demonstrate that SFACA operates via an efficient "activation-hydrolysis-dissociation-cyclic catalysis" acid generation mechanism, capable of continuously releasing hydrogen ions within the temperature range of 60～180 ℃. Its acid generation activity is effectively activated above 140 ℃, achieving an effective hydrogen ion concentration of up to 7.8 mol·kg−1. Furthermore, the acid concentration can be flexibly regulated by optimizing the agent-to-water mass ratio. The self-generated acid system constructed based on SFACA exhibits good compatibility and demonstrates efficient dissolution capability toward the primary mineral of carbonate rocks, CaCO3. The effective acid-rock reaction durations at 160 ℃ and 180 ℃ are 7 h and 4 h, respectively, with corresponding acid-rock reaction rates of 1.45×10−7 mol·cm−2·s−1 and 2.46×10−7 mol·cm−2·s−1, highlighting its long-lasting performance characteristics. Additionally, the system exhibits good corrosion inhibition, with dynamic corrosion rates on N80 steel coupons measured at 56.3 g·m−2·h−1 and 67.8 g·m−2·h−1 at 160 ℃ and 180 ℃, respectively. The high-temperature long-lasting self-generated acid system achieves high acidity, sustained release, and efficient etching under high-temperature conditions, providing reliable technical support for the efficient stimulation of deep high-temperature carbonate reservoirs at 160～180 ℃ range.
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表 1 不同剂/水比条件下SFACA水解实验结果
序号 碳酸钙溶
蚀量/g等效盐酸
浓度/%转化率/
%剂/水
质量比1 6.97 25.9 89.3 1∶0.1 2 7.67 23.7 98.3 1∶0.2 3 7.81 20.3 100.0 1∶0.4 4 7.82 19.2 100.1 1∶0.8 5 7.81 16.2 99.9 1∶1.0 6 7.82 11.4 100.1 1∶1.5 7 7.80 6.9 99.9 1∶2.5 
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表 3 不同酸液体系反应前后岩样成分变化
酸液类型 T/
℃矿物组分/% CaCO3 SiO2 Al2O3 Fe2O3 其他杂质 20%盐酸 160 0.6 58.5 23.5 12.2 5.2 180 0.3 59.8 24.2 11.5 4.2 自生酸 160 0.8 58.9 23.5 11.7 5.1 180 0.5 59.9 23.7 11.2 4.7
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表 4 选择性溶蚀定量分析结果
酸液类型 T/
℃CaCO3溶蚀率/
%难溶矿物富集系数 20%盐酸 160 99.4 28.6 180 99.7 28.9 自生酸 160 99.2 28.5 180 99.5 28.7
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表 5 酸岩反应动力学参数测试结果
序号 测试温度/
℃酸岩反应速率/
×10−7 mol·cm−2·s−1表观活化能/
kJ·mol−11 160 1.45 44.3 2 180 2.46
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表 6 不同温度下缓蚀性能评价结果
腐蚀类型 酸液体系 T/
℃P/
MPa缓蚀剂/
%平均腐蚀速率/
g·m−2·h−1静态腐蚀 20%盐酸 90 0.1 0.5 23.90 自生酸 0.5 1.35 动态腐蚀 20%盐酸 160 16.0 4.0 69.20 自生酸 4.0 56.30 20%盐酸 180 16.0 5.0 78.50 自生酸 5.0 67.80
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